Analysis of Spectra BRUKER

TopSpin
Analysis of 1D NMR Spectra
A Practical Approach to Simple and

Complex Spectral Structures
Version 001
NMR
Copyright © by Bruker Corporation
All rights reserved. No part of this publication may be reproduced, stored

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registered trademarks of their respective holders.
This manual was written by

Gerhard Hägele and Michael Engelhardt
© January 17, 2017 Bruker Corporation
Rheinstetten, Germany
P/N: H146197
DWG: 10000040609
For further technical assistance please do not hesitate to contact your

nearest Bruker dealer or contact us directly at:
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Internet: www.bruker.com
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Summary of Contents
1 Summary of Contents
1 Summary of Contents .................................................................................. 3
2 Contents ....................................................................................................... 5
3 Contact ........................................................................................................ 15
Book 1 ................................................................................................................. 17
4 Introduction ................................................................................................ 19
5 One-Spin System ....................................................................................... 39
6 Two-Spin Systems ..................................................................................... 57
7 Three-Spin Systems ................................................................................. 101
8 Four-Spin Systems .................................................................................. 257
Book 2 ............................................................................................................... 583
9 First Order Systems from Single Spins ................................................. 585
10 The Composite Particle Concept ............................................................ 589
11 Five Spins: CH3CH2R – A2B3, A2M3, ABC3, ABM3 Systems ................... 615
12 Seven and More Spins: C3 to C5 Alkyl Groups ..................................... 653
13 Five to Six Spins: H-F-Aliphatic Compounds ........................................ 681
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14 Five to Six Spins: Propene and Halopropenes .......................................687
15 Five Spins: ABC3 to ABX3 Crotonic Acid Ethylester ..............................695
16 Five or Ten Spins: AMNCX, AMRXY, AHMRX – Allyl Glycidyl Ether ....701
17 Five to Six Spins: ABCDE and ABCDEX – Butadienes ..........................711
18 Five to Seven Spins: Cycloalkanes .........................................................723
19 Four to Eight Spins: Cycloalkenes ..........................................................745
20 Five to Six Spins: Phenyl and Pentafluorophenyl Groups ....................751
21 Six Spins in C6H6-nFn .................................................................................807
22 Seven Spins: Quinolines ..........................................................................811
23 Seven to Twelve Spins: Polycyclic Aromatic Ring Compounds ..........819
24 Practical Examples from Multi-Spin Systems with Symmetry ..............831
25 Samples, Solvents, Temperature .............................................................851
26 Number of Transitions for Coupled Systems of Spins I = ½. ................883
27 Lorentzian Line Shape of a Singlet..........................................................885
28 Calculating Intensities for First Order Multiplets ...................................891
Appendix ............................................................................................................899
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Contents
2 Contents
1 Summary of Contents .................................................................................. 3
2 Contents ....................................................................................................... 5
3 Contact ........................................................................................................ 15
Book 1 ................................................................................................................. 17
4 Introduction ................................................................................................ 19
4.1 Some Introductory Remarks .................................................................................19
4.2 Developing the 47 Characteristic One- to Four-Spin Systems.............................33
5 One-Spin System ....................................................................................... 39
5.1 The A1 System – Spin System No. 1 ....................................................................39
5.2 Some Comments on Lorentzian Line Shapes of Resonance Signals..................42
5.2.1 The Lorentzian Singlet Absorption Signal Centered at ν0 ....................................43
5.2.2 The Lorentzian Singlet Dispersion Signal Centered at ν0 ....................................44
5.2.3 Integration of a Lorentzian Singlet Absorption Line..............................................45
5.3 Magnetic Resolution – the Real Experimental Line Shape in NMR Spectra .......47
5.4 Digital Resolution – the Density of Data Points in Experimental Spectra ............48
5.5 The Isotope Effect on Resonance Frequencies / Chemical Shifts .......................48
5.6 Lorentzian Absorption Spectra from Superimposing Singlet Lines ......................54
5.7 Practical Examples for 1-Spin Spectra .................................................................56
6 Two-Spin Systems ..................................................................................... 57
6.1 The AX System – Spin System No. 2 ...................................................................57
6.1.1 Evaluation of AX Doublets with Broad Lines (Low JAX/HWB Relation) ................62
6.1.2 Some Examples for Homonuclear AX Spin Systems ...........................................70
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6.1.3 A Heteronuclear AX Spin System with Rotational Isomerism ............................. 71
6.1.4 The AX Spin System in a Mono Fluorinated Cynnamic Acid C9H7O2F ............... 74
6.1.5 CHF=CHP(O)(OCH3)2 – a Heteronuclear RX System ......................................... 82

13
6.1.6 C-Enriched Molecules – the Observation of JCC and JNC in AX Type Spectra. . 83
6.2 The AB System – Spin System No. 3 .................................................................. 85
6.2.1 2,3-Dibromothiophene – a Typical Example for AB Spectra ............................... 89
6.2.2 Geometrical Solution of the AB Problem ............................................................. 90
6.2.3 Further Practical Examples of AB Systems are Shown Below ............................ 91
6.2.4 Sterically Hindered Ethanes CHRBr-CHR´Br ...................................................... 92
6.2.5 The CH2 Group in the Racemic Form of a Cyclo-Propane Derivative ................. 94
6.2.6 AB Spectra with Nucleus Specific Half Widths .................................................... 95
6.3 The A2 System – Spin System No. 4 ................................................................... 97
7 Three-Spin Systems .................................................................................101
7.1 The AMX System – Spin System No. 5 ............................................................. 102
7.1.1 Practical Examples ............................................................................................ 104

1
7.1.2 600 MHz H NMR Spectrum of 2-Furoic Acid – a Homonuclear AMX System . 105
7.1.3 Some Complications with Homonuclear AMX Spectra ..................................... 109
7.1.4 Determination of Signs of Coupling Constants J12, J13, and J23 ........................ 120
7.1.5 Double Resonance Experiments and Simulations ............................................ 122
7.1.6 Trifluorovinylchloride – a Homonuclear AMX with Minute ABC Character ........ 129
1
7.1.7 The 200 MHz H NMR Spectrum of Acrylonitrile in CDCl3. ............................... 131
7.2 The ABX System – Spin System No. 6 ............................................................. 132
7.2.1 Practical Examples for ABX Spectra – Homonuclear ABX and AXY Systems . 143
7.2.2 Practical Examples for ABX Spectra – Heteronuclear ABX Systems ............... 151
7.3 The AXX´ System – Spin System No. 7 ............................................................ 163
7.3.1 Practical Example .............................................................................................. 168
7.3.2 Further Examples: Tetrachlorobenzenes .......................................................... 173

2
7.3.3 Further Examples: JPP Coupling Constants in P-C-P Structures. .................... 174
3
7.3.4 Further Examples 3: JPP Coupling Constants in P-C-C-P Structures............... 175
7.4 The AX2 System – Spin System No. 8............................................................... 178
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7.4.1 The Homonuclear A2X F Spectrum of 1,1,2-Trichloro-1,2,2-trifluoroethane...180
7.4.2 The Hetero-Nuclear A2X Spectrum of Chlorofluoromethane CH2ClF ................183

19
7.4.3 94 MHz F NMR Spectra from the SF3 Part of C6F5-SF3 ..................................183
31
7.4.4 A2X Spectra from P NMR Studies of Tripolyphosphate Structures .................185
7.5 The ABC System – Spin System No. 9 ..............................................................188
7.5.1 Example 1: Ethane Derivates – tBu-CHX-CH2X (X = Cl, Br)..............................203

1
7.5.2 Example 2: 200 MHz H NMR Spectrum of Styrene in CDCl3 + TMS................206
1
7.5.3 Example 3: H NMR Spectrum of 1,2,4-Trichlorobenzene .................................208
1
7.5.4 Example 4: H NMR Spectrum of 1-Chloro-3-bromo-5-iodo-benzene ...............209
7.5.5 Example 5: Heterocyclic Derivatives – Thiophenes ...........................................211
7.5.6 pH-Dependence of Some ABC Spectra .............................................................212

1 31
7.5.7 500 MHz H{ P} Decoupled NMR Spectra of Vinyl Phosphonic Acid ...............214
7.5.8 Spectral Moments of ABC Spectra .....................................................................217
7.6 The ABB´ and the AA´B System – Spin System No. 10 ....................................223
7.6.1 Working through the AA´B Case as ABC Approximation ...................................225
7.6.2 A2B Approximation of the AA´B ..........................................................................226
7.6.3 Iteration of AA´B .................................................................................................228
7.6.4 The ABX Approximation .....................................................................................228
7.6.5 Practical Examples for AA´B and ABB´ Spectra ................................................232
7.7 The AB2 System – Spin System No. 11 .............................................................234
7.7.1 Practical Examples for AB2 Spectra and the Reverse A2B Case .......................241
31 1
7.7.2 AB2 System in P{ H} Spectrum of the Cyclotripolyphosphine [CH3P]3 ............245
7.7.3 The A2B Spectrum at 200 MHz from 1,2,3-Trichlorobenzene in CCl4 ................247
7.7.4 A2B and AB2 Spectra Approximating A2X and AX2 Cases .................................252
7.8 The AAÁ´´, AA´2, and A3 Systems – Spin System No. 12, 13, 14 .....................254
8 Four-Spin Systems .................................................................................. 257
8.1 Introduction .........................................................................................................257
8.2 The AMRX System – Spin System No. 15 .........................................................261
8.2.1 Practical Example 1: Furane Aldehyde ..............................................................261
8.2.2 Practical Example 2: N-Methyl-Pyrolidone .........................................................263
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8.2.3 Practical Example 3: CBrClF-CBrF-CF=CBrF ................................................... 267
8.2.4 Practical Example 4 and 5: Heteronuclear AMRX Systems .............................. 271
8.2.5 Practical Example 6: CF2=CF-PCl2 .................................................................... 274
8.2.6 Practical Example 7: AMRX and Chiral Discrimination ..................................... 276
8.3 The ABMX and Related AMNX, AMXY Systems – Spin System No. 16 ......... 281
8.3.1 Practical Example 1: The ABMX Case of 5-Fluoro-3-thiolene-2-one ................ 281
8.3.2 Practical Example 2: The Pair of Isomers ......................................................... 290
8.4 The A2MX and Related AM2X, AMX2 Systems – Spin System No. 18 .............. 301
8.4.1 Practical Example 1: Homonuclear AMX2 ......................................................... 302
8.4.2 Practical Example 2: Heteronuclear AM2X in CCl2=CH-CH2-P(O)(OEt)2 .......... 305
8.5 The ABXY System – Spin System No. 19 ......................................................... 306

1 31
8.5.1 200 MHz H{ P} NMR Spectrum of 2-Methoxy-1-oxa-3-thia-phospholane ...... 306
8.5.2 ABXY System in a CH2-CH2 Fragment of a P-Chiral Compound ...................... 317
8.5.3 Further Examples: Heteronuclear ABXY Spin Systems .................................... 323
8.6 The ABCX System – Spin System No. 20 ......................................................... 324
8.6.1 Example 1: Vinyl Fluoride and Acryloyl Fluoride ............................................... 326
8.6.2 Example 2: ABCX in CH2=CH-P(O)Cl2 .............................................................. 330
8.6.3 Example 3: ABCX in CH2=CH-P(O)(OiPr)2 and CH2Br-CHBr-P(O)(OiPr)2 ....... 336
8.6.4 Example 4: pH-Dependent ABCX Spectra ....................................................... 342
8.7 The ABX2 System – Spin System No. 23 .......................................................... 346

1
8.7.1 Practical Example 1: The H NMR Spectrum of Trans-CHCl=CH-CH2Cl ......... 346
8.7.2 Practical Example 2: ABX2 in Cis-1,2-Dichlorotetrafluorocyclopropane............. 353
8.8 The A2BX and the AB2X System – Spin System No. 24 ................................... 360
8.8.1 Practical Example 1: The A2BX Spectrum of 1-Fluoro-2,6-dichlorobenzene .... 360
8.8.2 Practical Example 2: AB2X Spectra from Organo Phosphorus Chemistry ........ 367
8.9 The [AX]2 System – Spin System No. 27........................................................... 368
8.9.1 Practical Examples for Heteronuclear [AX]2 Cases ........................................... 374
8.9.2 Practical Examples for Homonuclear [AX]2 Cases ............................................ 382
8.9.3 [AX]2 Systems with Rare Nuclei in Inorganic Chemistry.................................... 394
8.10 The AXX´2 System – Spin System No. 28 ......................................................... 395

13 31
8.10.1 Practical Example: An AXX´2 Spin System with A = C; X, X´ = P ................ 396
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8.10.2 Explicit Equations for Transition Frequencies and Intensities were Derived......411
8.11 The A2X2 System – Spin System No. 30 ............................................................413
8.12 The AX3 System – Spin System No. 31 .............................................................418
8.12.1 Practical Examples – Part 1 ...............................................................................419
8.12.2 Practical Examples – Part 2 ...............................................................................420
8.13 The ABCD System – Spin System No. 32 .........................................................421
8.13.1 Example 1: ABCD System in o-C6H4BrCl – 1-Bromo-2-chloro-benzene ...........421
8.13.2 Example 2: ABCD System in m-C6H4BrCl – 1-Bromo-3-chloro-benzene ..........423

1
8.13.3 Example 3: The H NMR Spectrum of 2-Sulfobenzoic Acid Ammonium Salt ....424
1
8.13.4 Example 4: H NMR Spectrum of Anthranilic Acid .............................................429
8.13.5 Some Further Examples for ABCD Systems ......................................................432
8.14 The ABC2 and Related AB2C, A2BC Systems – Spin System No. 34 ................433
8.14.1 Further Practical Examples ................................................................................438
8.15 The [AB]2 System Part 1: o-Disubstituted Benzenes – Spin System No. 37 .....440
1
8.15.1 Example 1: Centered H NMR Spectrum of o-Dibromobenzene .......................464
1
8.15.2 Example 2: A Non-Centered H NMR Spectrum of o-Dichlorobenzene ............466
8.15.3 Example 3: Substituent Effects in o-Disubstituted Benzene Derivatives ...........467
8.15.4 Example 4: Steric Strain and NMR Parameters .................................................468
8.15.5 Example 5: 7,7-Difluoro-benzo-cyclo-propene ...................................................470

1 31
8.15.6 Example 6: A H{ P} NMR Spectrum of o-Phenylene Phosphorochlorodite.....472
8.15.7 Example 7: ortho-Polyphenylenes ......................................................................472
8.15.8 [AX]2 – A Limiting Case of the [AB]2 System ......................................................480
8.16 The [AB]2 System Part 2: p-Disubstituted Benzenes – Spin System No. 37 .....487
1
8.16.1 Example 1: H NMR Spectra of 1-Bromo-4-chlorobenzene ...............................487
8.16.2 Example 2: 1-Bromo-4-nitro-benzene ................................................................493
8.16.3 Example 3: Some Halogenated 1,4-Disubstituted Benzene Derivatives ...........496
8.16.4 Example 4: Para-substituted Benzoic Acids p-R-C6H4-COOH...........................497
8.17 The [AB]2 System Part 3: Ethane Fragments HFP – Spin System No. 37 .........499
8.17.1 Example 1: 1-Bromo-2-chloroethane – Br-CH2 -CH2 -Cl ......................................500
8.17.2 Fixing the -CH2-CH2- Skeleton in Rigid Ring Systems .......................................514
8.17.3 [AB]2 in the Fixed Conformation of a Meta-Cyclophane .....................................515
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1 2
8.17.4 Chirality and Spectral Pattern in the R -CH2-CH2-R Skeleton ......................... 519
1 2 1 2
8.17.5 R -CF2-CF2-R - Fluorinated Analogues of R -CH2-CH2-R .............................. 522
8.17.6 Rigid Skeleton -CF2-CF2- in Substituted Perfluoro Cylobutenes ....................... 529

1 2
8.17.7 H-CP*2-CP*2-H - Phospha Analogues of R -CH2-CH2-R ................................. 533
8.18 The [AB]2 System Part 4: Dioxolanes – Spin System No. 37 ............................ 536
8.18.1 Example 1: Dioxolanes Undergo Dynamic Ring Inversion ................................ 536
8.18.2 Example 2: Ethylenesulphite ............................................................................. 538
8.18.3 Example 3: 2-Oxo-2-chloro-1,3-dioxa-2-phospholane ...................................... 543
8.19 The [AB]2 System Part 5: Final Remarks – Spin System No. 37 ...................... 544
8.19.1 [AB]2 and A2B2 Systems in Isomeric Cyclobutanes ........................................... 544

1
8.19.2 H NMR Spectra of Dichloro-1,3-butadienes ..................................................... 548
19
8.19.3 F NMR Spectra of Tetrafluoro-1,3-butadienes ................................................ 552
1
8.19.4 The H NMR [AB]2 Spectrum of Thiophene (Solution in CCl4) .......................... 554
1
8.19.5 H NMR [AB]2 Spectra of 4-Methoxypyridine and N-methyl-4-pyridone ............ 557
8.20 The A2B2 System – Spin System No. 40 ........................................................... 561
8.21 The AB3 Spectrum and the Related A3B Case – Spin System No. 41 .............. 570
8.21.1 Practical Examples ............................................................................................ 571
8.21.2 Analyzing AB3 Type Spectra .............................................................................. 575
8.21.3 Further Practical Examples ................................................................................ 577
8.22 The A4 and Related Spin Systems No. 42 to No. 47 ......................................... 579
Book 2 ................................................................................................................583
9 First Order Systems from Single Spins ..................................................585
10 The Composite Particle Concept .............................................................589
10.1 Spectra of Isolated Composite Particles ............................................................ 592
10.1.1 Example 1: The A2 Group .................................................................................. 593
10.2 Composite Particles AB4 and A4B...................................................................... 598
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10.3 Composite Particles A2B3 / A2X3 and A3B2 / A3X2 – Analysis of A2B3 Spectra ...601
31 1
10.3.1 The A2B3 Spectrum from [NiL5] [BF4]2 – P{ H} at Low Temperatures .............601
10.3.2 Rhodium Complexes [RhL5][BPh4] form A3B2X or A2B3X Systems ....................608
11 Five Spins: CH3CH2R – A2B3, A2M3, ABC3, ABM3 Systems ................... 615
11.1 A2B3 and A2X3 Spectra from Ethyl Compounds CH3CH2-R ................................615
11.2 Ethyl Groups Attached to Spin Active Units .......................................................620
11.3 Organophosphorus Compounds CH3CH2P(O)Cl2 / CH3CH2OP(O)Cl2...............622

1 31
11.4 Non-equivalence Effects in ABC3X H NMR and [ABC3]2X P NMR Spectra ...625
11.5 Non-equivalence Effects in Geminal Pairs of Enantiotopic Ethoxy Groups .......628
11.5.1 Example 1: C6H5P(OCH2CH3)2 ...........................................................................628
11.5.2 Example 2: C6Cl5P(OCH2CH3)2 ..........................................................................635
11.6 Aromatic Substituents Attached to C-Chiral Centers .........................................639
11.7 An ABM3X Spin System from 1-Chloro-2-fluoro-2-bromo-propane ....................652
12 Seven and More Spins: C3 to C5 Alkyl Groups ..................................... 653
12.1 CH3-CH2-CH2-R - n-Propyl Compounds .............................................................653
12.1.1 Example: CH3-CH2-CH2-CHO.............................................................................656
12.1.2 Example: CH3-CH2-CH2-P(O)Cl2 ........................................................................660
12.1.3 Exercise: n-Propylfluoride CH3CH2CH2F ............................................................666
12.2 i-Propyl Compounds ...........................................................................................667

1
12.2.1 AB6 and A6B Systems in H NMR Spectra of (CH3)2CH-SiR3 (R = Cl, Me) .......667
12.2.2 The AB6X System in (CH3)2CHP(O)Cl2 ..............................................................673

1
12.2.3 H NMR Spectra of Further Alkanes ...................................................................674
13 Five to Six Spins: H-F-Aliphatic Compounds ........................................ 681
13.1 ABCRX System in 1,2-Difluoropropionic Acid Ethylester CH2F-CHF-COOEt...681
13.2 6-Spin Systems from Fluorinated Ethanes C2H6-nFn and Acetones C3H6-nOFn: .685
14 Five to Six Spins: Propene and Halopropenes ...................................... 687
14.1 Propene and Chloropropenes ............................................................................687
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14.2 AM3X Spectra of Cis- and Trans-Isomers of 1-Chloro-2-fluoro-prop-(1)-ene ... 689
14.3 ABC3, ABX3, AMX3 Spectra of 2-Chloro-1,1,3,3,3-pentafluoro-prop-(1)-ene ... 690
14.4 ABCD3, AMNX3, AMRX3 Spectra of Perfluoropropene ...................................... 692
15 Five Spins: ABC3 to ABX3 Crotonic Acid Ethylester ..............................695
16 Five or Ten Spins: AMNCX, AMRXY, AHMRX – Allyl Glycidyl Ether ....701
16.1 The Allyl Group .................................................................................................. 703
16.2 The Glycidyl Group ............................................................................................ 707
17 Five to Six Spins: ABCDE and ABCDEX – Butadienes ..........................711
17.1 ABCDE Spectra of Three Isomeric Methoxybutadienes ................................... 711
17.2 ABCDE and ABCDEX Spin Systems in 2-Fluorobutadiene .............................. 714
17.3 The [ABC]2 - [AMX]2 in Perfluorobutadiene CF2=CF-CF=CF2 .......................... 717
18 Five to Seven Spins: Cycloalkanes .........................................................723
18.1 Five to Seven Spins – Cyclopropanes ............................................................... 723
18.1.1 Propyleneoxide – ABCD3 ................................................................................... 725
18.1.2 Epichlorhydrine and Related Structures – ABCDE............................................ 726
18.1.3 Epifluorhydrine – ABCDEX ................................................................................ 727
18.1.4 Dioxidobutane – [ABC]2 ..................................................................................... 728
18.2 Cyclobutanes: ABCDE at Lower Fields, AHKRX at Higher Fields .................... 731
19
18.2.1 F NMR Spectrum of 1,1,2-Trichloro-2,3,3,4,4-pentafluoro-cyclobutane ......... 731
18.2.2 The 6-Spin [AMX]2 Case of Cis-1,2-Dichlorohexafluorocyclobutane ................ 735
18.2.3 ABCDEX – AHKRTX in 1,2-Dibromo-2,3,3,4,4-pentafluorocyclobutane ........... 735
18.2.4 Seven Spins – A[BC]2DE from Cyanocyclobutane – Even at 800 MHz ............ 740
19 Four to Eight Spins: Cycloalkenes ..........................................................745
19.1 [A6[M]2X]2 – 1,1,2,2-Tetrafluoro-cyclobutene-3,4-bis-phosphonic Acid

Tetramethylester ................................................................................................ 746
19.2 Fluorocyclopentenes .......................................................................................... 749
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20 Five to Six Spins: Phenyl and Pentafluorophenyl Groups ................... 751
20.1 Five to Six Spins – Phenyl Groups in C6H5R ......................................................751

15
20.2 Spectra of C6H5R (R = H, CHO, F, N, CH3, CH=CH2) .....................................760
19
20.3 F NMR Spectra of Pentafluorophenyl Groups in C6F5R Compounds ..............791
19
20.3.1 Example 1: The 470.385 MHz F NMR Spectrum of C6F5Br ............................792
20.3.2 Example 2: Pentafluorobenzene C6F5H – the Case of an [AC]2BX Spectrum ...797
20.3.3 Long Range Coupling between Fluorines in C6F5 and Spins in Substituent R ..800
21 Six Spins in C6H6-nFn ................................................................................ 807
22 Seven Spins: Quinolines ......................................................................... 811
22.1 Simple 7-Spin Homonuclear First Order System in Perfluoroquinoline C9NF7 ..813
22.2 Complex 7-Spin Homonuclear Second Order System in Quinoline C9NH7 .......815
23 Seven to Twelve Spins: Polycyclic Aromatic Ring Compounds.......... 819

1
23.1 H NMR Spectrum of Naphthalene – an [AB]4 (D2h) System – 8-Spin Case .....819
H NMR Parameters of α-and β-Naphthyl Compounds C8H7R – 7-Spin Cases821

1
23.2
1
23.3 H NMR Spectrum of Anthracene – 10-Spin Case .............................................822
1
23.4 H NMR Spectrum of Thioxanthene Carbanion – 9-Spin Case.........................822
1
23.5 H NMR Spectrum of Phenanthrene – 10-Spin Case ........................................823
1
23.6 H NMR Spectrum of 3,4-Dibenzoperylene – 12 Spin System Fragmented .....825
24 Practical Examples from Multi-Spin Systems with Symmetry ............. 831

1
24.1 H Spectrum of Tetramethyldiphosphinedisulphide [(CH3)2P(S)]2 – X Part .......831
31
24.2 A Part of [AXn]2: The P NMR Spectrum of [(CH3O)2P(O)]2O ...........................834
24.3 Expansions to More Complex Problems: ...........................................................838
24.4 The [AXn]3 System: Molecules with Threefold Symmetry ...................................840
24.5 Fourfold Symmetry in [AX3]4 ? ............................................................................849
24.6 End of the Flagpole: Problems that cannot be Fully Analyzed and Simulated ..850
25 Samples, Solvents, Temperature ............................................................ 851
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26 Number of Transitions for Coupled Systems of Spins I = ½. ................883
27 Lorentzian Line Shape of a Singlet..........................................................885
28 Calculating Intensities for First Order Multiplets ...................................891
Appendix ............................................................................................................899
A.1 List of Compounds in Book I .............................................................................. 899
A.2 List of Compounds in Book 2 ............................................................................. 909
A.3 Suggested Readings ......................................................................................... 913
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Contact
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Book 1
Acknowledgements
Thanks are due to Miss Beate Rau (HHUD) who typed some of the introducing chapters and to Dr.
W. Peters / Mr. P. Behm (HHUD) and Dr. Michael Ackermann (Bruker Biospin) who provided
experimental NMR spectra. In a very early state, prior to the present manuscript, some theoretical
aspects of NMR spectroscopy were discussed with Dr. Hans Dolhaine (HHUD), which is
acknowledged gratefully. Further more specific acknowledgements were inserted in corresponding
chapters of this manuscript.
The final layout was done by Gilbert Cyppel. Gilbert´s extraordinary accuracy improved the
presentation of texts, tables, and figures considerably which is explicitly acknowledged by special
thanks from the authors. Last not least thanks are due to Anjana Ebner and Lisa Srbecky who
helped with checking the manuscript.
This project was supported by BRUKER Biospin, and hence our particular thanks are directed
towards Dr. T. Keller.
Düsseldorf / Rheinstetten, 17.12.2016 Gerhard Hägele / Michael Engelhardt
Laokoon (Photograph: G. Hägele)
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Introduction
4 Introduction
4.1 Some Introductory Remarks
60 years of research and development in theoretical and experimental methods have shed a multi
facetted light on nuclear magnetic resonance spectroscopy. Five Nobel prizes, for leading
discoveries in instrumental design supported by a battery of computing programs, give evidence of
an unbroken attraction of NMR as an indicative analytical tool for applications in physics, chemistry
and life sciences.
In the following chapters we will deal with the analysis of high resolution 1D NMR spectra, which is
one of the contemporary subdivisions of NMR. In the starting phase of the NMR sciences this field
gave rise to a multitude of basic contributions, which are worth rereading.
Studying chemistry underwent many changes during the decades gone by. The time dedicated to
concentrate on analytical chemistry and spectroscopic methods was reduced considerably. NMR
advanced to an ancillary method with automated measurements and automated evaluations. Less
attention is now paid towards basic concepts in spectral theory and experiments. Hence a wide
spread decrease in understanding complex NMR spectra is observed, combined with hesitations to
deal with “complicated NMR spectra”. Quite frequently miss-interpretations and erroneous citations
of NMR parameters in publications result.
Here we wish to present an easy way to understand the NMR spectra of practically relevant model
compounds and develop an intuitive comprehension of spectral patterns and underlying molecular
structures.
Notations for Spin Systems in NMR Spectroscopy
In 1957 POPLE, SCHNEIDER and BERNSTEIN introduced the classical ABPX-notation. Spins are
represented by capital letters, e. g.
ABCDEFG....KLMN..PQRS....XYZ
Letters with short distances in the alphabet indicate nuclei in second-order-relations while first-
order-relations are marked by letters separated by larger distances in the alphabet.
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Introduction
The classification in first- or second-order relations is governed by the spectral relation r i j :
∆ij
[1 ] rij =
Jij
wh er e ∆ij represents the difference of resonance frequencies νi and νj :
[2 ] ∆ij =νi − ν j
and Jij, the coupling constant between nuclei i and j.

A useful, but simplified, rule of thumb predicts the spectral character:
[3 ] rij >> 1 First-order spectra
[4 ] rij ≤ 1 Second-order spectra
Within this context, a number of basic concepts are introduced:
Isochrony - Anisochrony
If two spins within an ensemble have identical resonance frequencies
[5 ] νi =ν j
then they are called isochronous.
If
[6 ] νi ≠ ν j
they are anisochronous.
This does not imply any specific relations for the internal coupling constants between those spins
or coupling constants to external spins.
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Introduction
Magnetical Equivalence of Spins in Groups
If all n spins inside a group An have identical resonance frequencies and identical coupling
constants to all external spins Sk then the An spins are magnetically equivalent:
[7 ] νi =ν j for all i, j = 1 to n
[8 ] Jik = J jk for all i, j = 1 to n; for all k
A good example is methylene fluoride CH2F2 which is described as a classical A2X2 case: all proton
2
fluorine coupling constants JFH inside the molecule are identical.
Full equivalence exists if all internal coupling constants Jij inside the An group are identical.
Examples:
Three protons of the methyl group in methyl fluoride CH3F form the A3-group of a total A3X spin
2
system. These methyl protons are magnetically equivalent and fully equivalent, since all JHH
couplings (H-C-H) inside the methyl group are identical.
Nine protons of three methyl groups in t-butyl fluoride [CH3]3CF form the A9 group of a total A9X
spin system. All protons are magnetically equivalent but not fully equivalent. Two different
2 4
types of coupling constants exist inside the A9 group: JHH (H-C-H) and JHH (H-C-C-C-H).
Internal couplings of a group do not affect the spectral habitus of high resolution 1D NMR spectra
of isotropic solutions. In such situations a meticulous differentiation between magnetical and full
equivalence is not of practical relevance. NMR spectroscopy of anisotropic solutions will reveal
the phenomenon of magnetical and full equivalence, but here we will not deal with this more
specialized topic.
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Introduction
Chemical Equivalence in Symmetric Spin Systems
Numerous molecular structures are affiliated with magnetically non-equivalent but isochronous
spins following specific symmetry criteria with respect to inherent coupling constants.
Typical examples are shown with three isomers of difluoroethylene C2H2F2:
H H H F H F
C C C C C C
F F F H H F
1 2 1 4 1 3
3 4 3 2 2 4
C2 Ci C2
Spins in pairs are chemically equivalent. They are isochronous but have different couplings to
partners as shown in subsequent relations. Resonance frequencies follow:
[9 ] ν1 =ν2 a nd ν3 =ν4
while coupling constants obey:
[1 0] J13 = J24 a nd J14 = J23
but
[1 1] J13 ≠ J14 a nd J23 ≠ J24
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Introduction
In 1957 POPLE, SCHNEIDER and BERNSTEIN introduced a notation A2X2 for this type of four
spin systems in C2H2F2 and in CH2F2. The PSB-notation neglected the significant difference
between chemical and magnetical equivalence.
In 1958 RICHARDS and SCHAEFER suggested, to indicate chemically equivalent spins with ´ ,
e.g.: AA´XX´ for H2C=CF2 while CH2F2 remained as A2X2.
In 1960 DIEHL and POPLE presented a different view and suggested to indicate magnetically
* *
equivalent spins in groups by * . A2 X2 was used for CH2F2 while H2C=CF2 remained as A2X2.
The hitherto mentioned notations exhibit considerable disadvantages for complicated multi spin
cases with symmetry properties.
In 1970 a better notation was introduced by HAIGH, which will be discussed in some details in the
subsequent section.
Symmetrical spin systems are indicated by square brackets followed by a subscript and symmetry
symbol. This is visualized for a few examples below:
H F
H Cl H H
o-Dichlorobenzene 1,3,5-Trifluorobenzene
[AB]2 H Cl F F [AX]3
H H
Symmetry operations transfer resonance frequencies and coupling constants into corresponding
symmetry equivalents. The symmetry operation is indicated by a corresponding point group, given
in round brackets. This notation excludes ambiguities. Hence [AB]2 (C2) describes o-
dichlorobenzene while [AX]3 (C3v) stands for 1,3,5-trifluorobenzene.
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Introduction
Square brackets stand for one type of symmetry operation and can be repeated in pairs for each
symmetry operation, as shown for the example of cyclobutene:
H1 H6
H3 H5
C C
H1 H6
C C
H2 H4
H2 H H4 H
3 5
Cyclobutene C4H6 [[A]2B]2
Intra molecular rotation may lead to symmetrisation. Such systems are indicated by an additional
symbol: (rot). We will meet this situation in 1,2-disubstituted ethanes, e. g. in structures likes X-
CH2-CH2-Y, which give rise to [AB]2 systems.
H1 H3
Cl C C Br
H2 H4
Cl-CH2-CH2-Br [AB]2 (Cs, rot)
Further examples are shown in the following table below and will be discussed in subsequent
chapters.
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Introduction
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25
Introduction
The HAIGH notation does not deal with cases of accidental isochrony in non-symmetrical spin
systems.
Such a case may show up in practical NMR spectroscopy, e. g. in fragments of rotating ethanes
like CHR R -CH2R (R ≠ R ), where the geminal pair of CH2 protons in this chiral compound in
1 2 3 1 2
principle should exhibit specific non-symmetrical resonance frequencies νH and coupling constants
3
JHH. But if corresponding resonance frequencies are accidentally isochronous than ABB´ systems
1 2 3
are observed and not the expected ABC case in the skeleton of CHR R -CH2R . Only for such
situations we will retain the spin indicators ´. At an advanced stage of spectral analysis, we will see,
that the apparent spin symmetry might be higher then the atom symmetry given in a molecule.
Quite frequently doubts occur about the notation of rotationally averaged spin systems. Then
MORTIMER´s concept of highest symmetry of rotamers will help. E. g.: The model systems like
X-CH2-CH2-Y or X-CF2-CF2-Y may be described by two classical gauche and one trans conformer.
Free rotation will give rise to apparent [AB]2 (Cs, rot) spectra. A hypothetical frozen trans rotamer
would exhibit [AB]2 (C2) spectra while both gauche conformers are described by ABCD type
spectra.
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Introduction
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27
Introduction
MORTIMER 2
Equivalence in Non-rigid Molecules - Conformation of Highest Symmetry
Example 3
H2 H3 H2 H3
H1 C H4 H1 C H4
C C C C
R1 R2 R1 R2 R1 R2 R2 R1
R1 H2 R1 R1 H2 R2
H1 C C C H4 H C C C H4
R2 H3 R2 R2 H3 R1
Example 4
H2 R3 H2 R3
H1 C H3 H1 C H3
C C C C
R1 R2 R1 R2 R1 R2 R2 R1
R1 H2 R1 R1 H2 R2
H1 C C C H3 H C C C H3
R2 R3 R2 R2 R3 R1
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Introduction
Graphical Symbols and Spectral Habitus of Spin Systems
Once we have trained spectral analysis we will be able to develop an intuitive understanding of
spectral patterns. Using graphical symbols for one- to three-spin systems will help in this beginning
phase of our studies:
Connections Frequencies Coupling

anisochronous weak
anisochronous strong
isochronous strong
One-Spin System
Symbol System Number
1 A 1
Two-Spin Systems
1 2 AX 2
1 2 AB 3
1 2 A2 4
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Introduction
Three-Spin Systems
AMX 5
2 3
ABX 6
AXY
2 3
AA´X 7
AXX´
2 3
A2X 8
AX2
2 3
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Introduction
ABC 9
2 3
AA´B 10
ABB´
2 3
A2B 11
AB2
2 3
AAÁ´´ 12
2 3
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31
Introduction
A2A´ 13
AA´2
A´ A´´
A3 14
2 3
Some Special Cases with Vanishing Coupling Constants: Jik = 0

AMX 5
2 3
ABX 6
AXY
2 3
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Introduction
AA´X 7
AXX´
2 3
ABC 9
2 3
AA´B 10
ABB´
2 3
For speedy identification in forthcoming chapters spectra and spin systems will be marked
with symbols given above.
4.2 Developing the 47 Characteristic One- to Four-Spin

Systems
The spin active nuclei of a molecule form a spin system which is described - as shown above - by
capital letters from the alphabet and characterized by a set of spectral relations rij and further
symmetry criteria.
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Introduction
If rij >> 1 the total system yields a simple first order spectrum. In general spin systems may show
second order spectra and hence are more complex to understand.
Aim of the present paper is, to study systematically the easily understandable cases. Some will be
prone to Direct Analysis, some will need more laborious work involving computing.
We will learn that sub-spectral analytical approaches and other suitable approximations lead to
NMR parameter sets which can be refined by calculations using a variety of computer programs.
Iteration and simulation will confirm our knowledge about more complex NMR spectra and
corresponding molecular structures.
The major part of this armory of spectroscopic relevant concepts and techniques to analyze 1D
NMR spectra is accessible via studies of one- to four-spin systems. The following chapter
describes the systematic deduction of 47 one- to four-spin systems spanning the range from trivial
A1 to more complex ABCD cases. Additional knowledge will be gained from studies of selected
higher spin systems leading to the problems of larger molecules, more complex symmetries,
overlapping spectra of individual fragments and the benefits of automated spectral analysis.
The systematic deduction of 47 spin systems from A1 to ABCD is achieved by application of
five characteristic operations OPi which convert a start system SSstart into a subsequent end
system SSend:
SSstart 
OPi
→ SSend
The five characteristic operations OPi:
OPi additional spin Sk obeys

Operation 1 rik >> 1 First order relation.
Operation 2 rik ∼ 1 Second order relation.
Operation 3 rik = 0 Sk is isochronous with Si.
Sk is isochronous with Si and coupling
Operation 4 rik = 0 constants follow symmetry criteria of chemical
equivalence.
Sk is isochronous with Si and coupling
Operation 5 rik = 0 constants follow symmetry criteria of
magnetical equivalence.
Applying those principles to 1 one-spin system A1 leads to 3 two-spin systems AX, AB and A2.
Each of those three two-spin systems can be subjected to operations to derive effectively
10 three-spin systems. And finally 33 four-spin systems are obtained.
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Introduction
After applying those deduction-principles and excluding redundant results from these methods are
listed below as originally new spin systems and are marked in red.
Nspins Spin Systems Ntotal Nrelevant

1 1-Spin System 1 1
2 2-Spin Systems 3 3
Not all of those 47 cases are important for the manuscript presented here. Practically relevant
systems, which we might meet during laboratory work, are marked in blue.
The 47 One- to Four-Spin Systems
Start Operation End Spin System No. No.

SSstart SSend New Relevant
nihil 1 A A 1 1
A 1 AX AX 2 2
2 AB AB 3 3
5 A2 A2 4 4
AX 1 AMX AMX 5 5
2 ABX ; AXY ABX 6 6
3 AA´X ; AXX´ AXX´ 7 7
5 A2X ; AX2 AX2 8 8
AB 1 ABX
2 ABC ABC 9 9
3 AA´B ; ABB´ ABB´ 10 10
5 A2B ; AB2 AB2 11 11
A2 1 A2X ; AX2
2 A2B = AB2
3 AAÁ´´ AAÁ´´ 12
3 A2A´ ; AA´2 AA´2 13
5 A3 A3 14 14
AMX 1 AMPX AMPX 15 15
2 ABMX ABMX 16 16
3 AA´MX AA´MX 17
5 A2MX A2MX 18 18
ABX 1 ABMX
2 ABXY ABXY 19 19
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Introduction

2 ABCX ABCX 20 20
3 ABXX´ ABXX´ 21
3 ABB´X ABB´X 22
5 ABX2 ABX2 23 23
5 AB2X AB2X 24 24
AXX´ 1 AMXX´
2 ABXX´
2 AXXÝ
3 AXX´X´´ AXX´X´´ 25
3 AA´XX´ AA´XX´ 26
4 [AX]2 [AX]2 27 27
5 AXX´2 AXX´2 28
5 A2XX´ A2XX´ 29
AX2 1 AMX2
2 ABX2
2 AX2Y
3 AA´X2
3 AX2X´
5 A2X2 A2X2 30 30
5 AX3 AX3 31 31
ABC 1 ABCX
2 ABCD ABCD 32 32
3 ABCC´ ABCC´ 33
5 ABC2 ABC2 34 34
ABB´ 1 ABB´X
2 ABBĆ
3 AA´BB´ AA´BB´ 35
3 ABB´B´´ ABB´B´´ 36
4 [AB]2 [AB]2 37 37
5 A2BB´ A2BB´ 38
5 ABB´2 ABB´2 39
AB2 1 AB2X
2 AB2C
3 AA´B2
3 AB´B2
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Introduction

5 A2B2 A2B2 40 40
5 AB3 AB3 41 41
AAÁ´´ 1 AAÁ´´X
2 AAÁ´´B
3 AAÁ´Á´´´ AAÁ´Á´´´ 42
4 [[A]2]2 [[A]2]2 43 43
5 AAÁ´´2 AAÁ´´2 44
AA´2 1 AA´2X
2 AA´2B
3 AA´2A´´
5 A2A´2 A2A´2 45
5 AA´3 AA´3 46
A3 1 A3X
2 A3B
3 A3A´
5 A4 A4 47 47
Summing up the 47 One- to Four-Spin Systems
Nspins Spin Systems Ntotal Nrelevant

1 1-Spin System 1 1
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37
Introduction
Practically relevant systems, which we might meet during laboratory work, are marked in blue, less
important ones in red. An oversight is given in the following table:
Spin system No. Spin system No.
A 1 ABX2 23
AB2X 24
AX 2 AXX´X´´ 25
AB 3 AA´XX´ 26
A2 4 [AX]2 27
AXX´2 28
AMX 5 A2XX´ 29
ABX 6 A2X2 30
AXX´ 7 AX3 31
AX2 8 ABCD 32
ABC 9 ABCC´ 33
ABB´ 10 ABC2 34
AB2 11 AA´BB´ 35
AAÁ´´ 12 ABB´B´´ 36
AA´2 13 [AB]2 37
A3 14 A2BB´ 38
ABB´2 39
AMRX 15 A2B2 40
ABMX 16 AB3 41
AA´MX 17 AAÁ´Á´´´ 42
A2MX 18 [[A]2]2 43
ABXY 19 AAÁ´´2 44
ABCX 20 A2A´2 45
ABXX´ 21 AA´3 46
ABB´X 22 A4 47
It is tempting but tedious and unpractical to continue this principle in order to develop the higher
multi spin systems. It is more meaningful to study some selected and practically relevant cases
together with characteristic molecular structures at an advanced state of this manuscript.
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One-Spin System
5 One-Spin System
5.1 The A1 System – Spin System No. 1
The NMR spectrum of a compound having one spin-active proton e.g. CHCl3, consists of a singlet
line centered at the resonance frequency ν A [Hz] following the classical Larmor equation:
e
γA
[1]
ν = (1- σ A )Bo
e
2π
A
where γA stands for the magnetogyric ratio for the nuclear type of spin A, σA for the shielding
constant of A in this particular compound, B0 for the magnetic field strength (more correct: the flux)
inside the probe head of the corresponding magnet. For a magnetic field of 11.74 Tesla protons
resonate in the region of 500 MHz. Since it is inconvenient to measure high frequencies in high
precision, an auxiliary frequency νRe is introduced which originates from a reference or standard
compound R:
γR
[2]
ν Re = (1- σ R )Bo
2π
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39
One-Spin System
For γA = γR = γ the difference of frequencies νeA − νRe is given by
γ
[3]
ν Ae −ν Re = (σ R - σ A )Bo
2π
This relative frequency is conveniently smaller - in the Hz to KHz range for protons and
heteronuclear spins. It is even more convenient to introduce a dimensionless parameter which may
be regarded as a reduced frequency.
ν Ae −ν Re σ R - σ A
[4]
= ≈σR -σ A
νRe
1− σ R
Since the shielding constants are found in the order of 10 we can derive the chemical shift δA
-6
[ppm] of nucleus A with respect to the reference R:
ν e
− ν e
[5] =δA A R
⋅106
νRe
In forthcoming experimental and simulated spectra we will NOT use directly the actual
experimental resonance frequencies νeA and νRe and similar parameters.
Relative frequencies like
[6] ν=
A ν A −ν R
e e
and
[7] ν R =ν Re −ν Re = 0
will be measured and used. And it is this νA which will be called resonance frequency in all
programs for analysis and simulation of NMR spectra.
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40
One-Spin System
The following figure shows a simulated singlet line centered at νA = 0 and having ideal Lorentzian
line shape (no noise, no spikes, and no impurities):
Figure 1 : A1 spectrum, arbitrarily centered at νA = 0.
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One-Spin System
5.2 Some Comments on Lorentzian Line Shapes of Resonance

Signals
Fourier transform of an FID signal leads to two characteristic functions: the absorption and the
dispersion signals. For routine elucidation of chemical structures it suffices to study the absorption
signal. In some cases with broad lines it may be useful to look into the dispersion function. A
normalized plot for the absorption and the dispersion signals is shown below:
Figure 2 : Absorption and Dispersion signals. Intensities normalized to extrema at ± 1. Spectral half
width HWB = 1Hz (indicated by arrow ←→).
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One-Spin System
5.2.1 The Lorentzian Singlet Absorption Signal Centered at ν0
The frequency dependent intensity of an absorption signal is proportional to the function A, which is
described by a simplified notation.
1
T2 πHWB
[8] A= A=
1 + 4π2T22 (ν0 − ν )2 1+ 4 ( ν − ν )2
2 0
HWB
The following variables are used. T2 : transverse relaxation time [sec]. HWB : spectral half width
[Hz] of the Lorentzian line. ν0 : central resonance frequency [Hz] of transitions.
ν : variable frequency [Hz].
Remember: The transverse relaxation time T2 is inversely proportional to the spectral half width
HWB:
1
[9] T2 =
πHWB
A is an even function of the frequency ν giving rise to a symmetric line shape centered around ν0 .
A has a maximum of
1
[10] A max = T2 A max =
πHWB
at
[11] ν =ν0
and a minimum of
[12]
Amin = 0
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43
One-Spin System
at
[13] ν = ±∞
Hence the intensity at half height is given by
T2 1
[14] A1/ 2 = A1/ 2 =
2 2πHWB
and this is true for
HWB
[15] ν1/ 2 =ν0 ±
2
5.2.2 The Lorentzian Singlet Dispersion Signal Centered at ν0
The frequency dependent intensity of a dispersion signal is proportional to the function D which is
described by a simplified notation:
1
( ν − ν)
T22 (ν0 − ν ) π HWB2 0
2
[16] D = D=
1 + 4π2T22 (ν0 − ν )2 1+
4
( ν 0 − ν)2
2
HWB
The intensity D is an uneven function of the frequency ν giving rise to an inversion center at ν0 and
reaches zero for
[17] ν =ν0 and ν = ±∞
D shows a maximum at
HWB
[18] νmax =ν0 −
2
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44
One-Spin System
and a minimum at
HWB
[19] νmin =ν0 +
2
Hence the difference between the frequencies of both extrema is HWB.

Note: The spectral half width of a very broad line is accessible with better accuracy using the
dispersion mode.
The algebraic properties of absorption and dispersion modes and corresponding derivatives for
first, second and third order with respect to frequency were studied and described in details in
Appendix 27. Pay attention towards the second derivative of absorption, which will be a diagnostic
tool in separating overlapping lines in advanced problems of this manuscript.
5.2.3 Integration of a Lorentzian Singlet Absorption Line
The experimental intensity of a Lorentzian absorption line is proportional to the number of spins Ns
inside the NMR sample. Using a simplified notation:
NS
[20] A=
NS T2
A= πHWB
1 + 4π T22 (ν0 − ν)2
2
1+
4
( ν 0 − ν )2
2
HWB
A can be abbreviated to:
C
[21] A=
1 + B2 (ν 0 − ν )2
using
2
[22] B =2π T2 =
HWB
NS
[23] =C N=
S T2
π HWB
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45
One-Spin System
An integral of the Lorentzian absorption function in a frequency interval from a to b is described by:
b b
C C
=
[24] A dν ∫
a
∫ 1+ B =
a
(ν − ν )
2
0
dν 2
B
{arctan(B(b − ν 0 ) − arctan(B(a − ν 0 )}
Hence an integral spanning the range from -∞ to + ∞ is given by;
+∞
C C
[25]
∫ 1 + B2 (ν0 − ν)2
−∞
d ν=
B
π
Defining a relative integral ρ which is symmetrically placed within in the range
from (ν0 - ∆) to (ν0 + ∆) according to
ν0 = + ∆
A
∫
ν0 = − ∆
1+ B ( ν0 − ν)2
2
[26] ρ = ν0 = + ∞
A
∫
ν0 = − ∞
1+ B ( ν0 − ν)2
2
leads to
2
[27] ρ= ⋅ arctan( ∆ B )
π
Finally the inverse function is given by
1 π
[28]=∆ tan( ρ)
B 2
HWB π
=
[29] ∆ tan( ρ)
2 2
which allows estimating the accuracy of an integral. The Lorentzian line is integrated in an interval
of 2 ∆ HWB - symmetrically placed around ν0.
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One-Spin System
As the following figure will show, an accuracy of ρ is achieved for the reduced integral.
Figure 3 : X-axis: Accuracy of reduced integral ρ. y-axis: ∆ = number of HWBs symmetrically placed
to left and right of ν0.
For an accuracy of 0.99 (99%) of the reduced integral an interval of 64 HWBs is needed. This
corresponds to 32 HWBs symmetrically placed on either side of the singlet at centered at ν0. Using
an interval of 14 HWBs reduces the accuracy to 0.95 (95%). Please bear this in mind when
evaluating integrals.
5.3 Magnetic Resolution – the Real Experimental Line Shape in

NMR Spectra
In practice, experimental line shapes in high-resolution (HR) NMR spectra may deviate from the
pure Lorentzian profile. The magnetic field covering the NMR sample is rarely fully homogeneous
and we “see” the superposition of several weighted resonances originating from slightly different
effective B0 values. This real line shape can be improved by careful (time consuming) shimming.
Ask your operator to do so – if you need good NMR spectra. In principle it is possible to
decompose the real line shape and extract correct data for resonance frequency, intensity and
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47
One-Spin System
spectral half width. One useful approach is to describe the real line shape as a superposition of
Lorentzian and Gaussian lines.
For details read: W. Dietrich, B. Fröhlich, U. Günther and M. Wiecken; Fresenius Z. Anal. Chem.
316, 227-230 (1983) and references quoted herein.
Programs simulating NMR spectra using real line shapes are not in common practice up to now.
Hence we will deal with idealized Lorentzian line shapes and come back to this spectral problem in
forthcoming chapters.
5.4 Digital Resolution – the Density of Data Points in

Experimental Spectra
The quality of your spectra depends on the “digital resolution” - effectively the number of data
points used to describe the spectral range. But in fact it is NOT the number of points per Hz which
governs the quality of experimental spectra – it is the number of points per spectral half width. For
good spectra arrange for about 15 data points per spectral half width! This topic will be discussed
in detail during the course of spectral iterations using commercially available programs, e. g.
TopSpin and DAISY.
5.5 The Isotope Effect on Resonance Frequencies / Chemical

Shifts
1
While CHCl3 exhibits a neat singlet in H NMR spectra the analogous CFCl3 yields a characteristic
19
four line pattern in F NMR spectra. We see the superposition of four singlets originating from four
isotopomeric molecules
35 35 37 35 37 37
CF Cl3 CF Cl2 Cl CF Cl Cl2 CF Cl3.
reference
19 35 37
The second F NMR peak (from left) corresponds to CF Cl2 Cl, and actually this is the
resonance which is defined to δF = 0.0 ppm if CFCl3 is used as a standard in

19
F NMR.
19
A. KENTWRIGHT (Durham) kindly provided an experimental F NMR spectrum (see below) from
CFCl3 in CDCl3 measured at 470.967 MHz).
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One-Spin System
Frequencies obtained by peak picking
[Hz]
19
Figure 4 : 470.967 MHz F NMR spectrum showing four isotopomers from CFCl3. Peak picking from
35 35 37 35 37 37
left to right: a) CF Cl3, b) CF Cl2 Cl, c) CF Cl Cl2, d) CF Cl3.
Frequencies and chemical shifts obtained by deconvolution of this spectrum
No. Frequency Shift Width Intensity Integral

(Hz) (ppb) (Hz) (rel.)
1 +3.02 +6.412 1.27 5.494160e+003 45.40
2 0 0 1.23 5.269637e+003 42.34
3 -2.99 -6.349 1.16 1.566528e+003 11.86
4 -6.02 -12.78 0.45 1.373817e+002 0.40
Remember: The isotope shift is presented in ppb (not in ppm).

19 1 19
F spins are more sensitive to isotope effects (and other neighbor effects) than H, making F a
widely used sensor for molecular structures.
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Some Remarks Concerning the 35Cl / 37Cl Isotope Effect for Other Compounds
35 37
Chlorine exists as a natural mixture of Cl and Cl isotopes in a ratio of 0.7553 : 0.2447. Hence
we expect chloro isotopomers for a variety of compounds having nCl chlorine atoms in the
molecule. And indeed we are able to see marked isotope effects when observing the appropriate
nuclei as given in the following table:
nCl Example Observe

19
1 Cl CF3Cl F NMR
19
2 Cl CF2Cl2 F NMR
19
CFCl3 F NMR
3 Cl 31
PCl3 P NMR
13
4 Cl CCl4 C NMR
5 Cl no ex. known -
- 195
6 Cl [PtCl6] Pt NMR
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One-Spin System
35 37
The Statistical Probability of Cl / Cl Isotopomers is Listed in the Following Table:
35 37
nCl n( Cl) n( Cl) Isotopomer Sum AW* Stat. Prob.**
1 1 0 1 34.96885 0.75530
1 0 1 2 36.94740 0.24470
2 2 0 1 69.93770 0.57048
2 1 1 2 71.91625 0.36964
2 0 2 3 73.89480 0.05988
3 3 0 1 104.90655 0.43088
3 2 1 2 106.88510 0.41879
3 1 2 3 108.86365 0.13568
3 0 3 4 110.84220 0.01465
4 4 0 1 139.87540 0.32545
4 3 1 2 141.85395 0.42175
4 2 2 3 143.83250 0.20495
4 1 3 4 145.81105 0.04427
4 0 4 5 147.78960 0.00359
5 5 0 1 174.84425 0.24581
5 4 1 2 176.82280 0.39818
5 3 2 3 178.80135 0.25800
5 2 3 4 180.77990 0.08359
5 1 4 5 182.75845 0.01354
5 0 5 6 184.73700 0.00088
6 6 0 1 209.81310 0.18566
6 5 1 2 211.79165 0.36090
6 4 2 3 213.77020 0.29231
6 3 3 4 215.74875 0.12627
6 2 4 5 217.72730 0.03068
6 1 5 6 219.70585 0.00398
6 0 6 7 221.68440 0.00021
*) Sum AW: sum of atomic weights of all chlorine atoms. **) Stat. Prob.: Statistical probability of
isotopomer.
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One-Spin System
37 19
Consider the example of CFCl3 shown above. The heavier isotope Cl shifts the F NMR signal to
19 35
high field by ca. 6.4 ppb with respect to the F NMR signal from the Cl isotopomer. Using the
data from CFCl3 we can estimate the spectral patterns for compounds having nCl chlorine nuclei as
shown below. The patterns will be scaled by individual nuclear specific parameters but in principle
will appear similar to the figures given below and indeed were found so for PCl3 and other
examples.
8 4 0 -4 -8 8 4 0 -4 -8
(Hz) (Hz)
1 Cl 2 Cl
8 4 0 -4 -8 8 4 0 -4 -8
(Hz) (Hz)
3 Cl 4 Cl
8 4 0 -4 -8 8 4 0 -4 -8
(Hz) (Hz)
5 Cl 6 Cl
35 37
Figure 5 : Hypothetical splitting patterns for Cl/ Cl-isotopomers for molecules holding 1 to 6 chlorine
atoms.
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One-Spin System
35 37 31
This Cl/ Cl-isotope effect is observed quite frequently, for example in the P NMR spectrum of
phosphorous trichloride PCl3:
31
Figure 6 : P NMR spectrum of phosphorous trichloride PCl3.
195 2-
or the Pt NMR spectrum of the hexachloroplatinate anion [PtCl6] , see the left figure below.
195 2- 2
Figure 7 : Pt NMR spectra of isotopomers. Left: [PtCl6] . Right: [PtBr6] .
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One-Spin System
195
The heavy nucleus Pt is sensitive to isotope effects induced in the hexabromoplatinate anion
2 79 81
[PtBr6] by both natural isotopes of bromine ( Br, 50.54%; Br, 49.46%), see the right figure
above.
79 81 2-
Calculate the statistical distribution of isotopomers [Pt( Br)i( Br)6-i] (i = 0 to 6). A good first order
guess is: both natural bromine isotopes are almost equi-populated, hence we expect a spectral
pattern similar to the A part of an AX6 system consisting of spins with I = 1/2: basically a septet.
And this is similar to what we see right above.
5.6 Lorentzian Absorption Spectra from Superimposing Singlet

Lines
The Lorentzian line shape for a superposition of nL spectral lines with resonance frequencies νi,
intensities Ii and line specific half width HWBi is described by:
nL
Ii T2
[30] =
Int( ν ) const ⋅ ∑
i = 1 1+ 4 π T2 ( ν i − ν )
2 2 2
1
[31] HWBi =
π T2i
Ii
nL
π HWBi
[32] =
Int( ν ) const ⋅ ∑
ν −ν 2
i =1
1+ 4 ( i )
HWB i
The most simple case of one singlet line (nL = 1) was discussed above. Consider two singlets,
centered at ν1 = +50.0 Hz and ν2 = -50.0 Hz resp.. Intensities are arbitrarily chosen to be

I1 = 1.0 and I2 = 2.0 resp.. Both lines have a common half width of HWB = 1.0 Hz.
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One-Spin System
A corresponding spectrum was simulated and then integrated as shown below:
1.00 Integrals 2.00
100
80
60
40
20
0
80 40 0 -40 -80
(Hz)
Figure 8 : Integration of two well separated singlets. Theoretical intensity ratio 1:2.
Integrals are practically reliable, if the symmetric integration range spans 64 HWB for each line and
both lines are separated by more or equal than 64 HWB. If the separation is less than 64 HWB
then the integrals are less accurate as shown below.
1.00 Integrals 1.96
100
80
60
40
20
0
80 40 0 -40 -80
(Hz)
Figure 9 : Integration of two insufficiently separated singlets. Theoretical intensity ratio 1:2.
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One-Spin System
Bear this in mind, when you use integrals for structural analysis or quantitative analysis of your
compounds. In such cases it might be better to use the deconvolution tool of your program for data
evaluation, e. g. TopSpin.
5.7 Practical Examples for 1-Spin Spectra
Example Spin Example Spin Example Spin

1 19 31
CHCl3 H CFCl3 F PCl3 P
1 19 31
C2HCl3 H C6FCl11 F H3PO4 P
1
C6HCl5 H
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Two-Spin Systems
6 Two-Spin Systems
6.1 The AX System – Spin System No. 2
1 2
AX r » 1
This first-order system consists of two doublets, centered around ν A or ν X resp., each split by a
repeated spacing, the coupling constant J A X . See the figure below. The sign of J A X does not affect
the spectral pattern. Hence the repeated spacing provides the absolute value of J A X only.
Figure 10 : Hypothetical AX spectrum
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Two-Spin Systems
Those four equi-intense lines are enumerated from left to right (high to low frequency) by symbols
ν1 to ν4.
A more general notation uses the “effective Larmor frequencies” indicated by small letters for each
nucleus separately as shown below:
Figure 11 : Hypothetical AX spectrum
1
[1]
νa =ν A + JAX
2
1
1
[2]
νa =ν A − JAX
2
2
1
[3] ν x1 =ν X + JAX
2
1
[4]
ν x =ν X − JAX
2
2
[5] Ia= Ia= Ix= Ix= 1

1 2 1 2
The spectrum of the A part is congruent with that of the X part. For spectral analysis the following
algebraic formulae are used
1
[6]
ν A= (νa + νa )
2 1 2
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Two-Spin Systems
1
[7]
ν X= (ν x + ν x )
2 1 2
[8] JAX = (νa1 − νa2 ) = (ν x1 − ν x2 )
Two different types of AX systems are defined, where A and X are of identical or non-identical spin
types.
homonuclear AX γA = γX
heteronuclear AX γA ≠ γX
Practical examples are shown in the following tables:
Homonuclear AX Systems
Structure MHz A-nucleus X-nucleus

2,3-Dibromothiophen 500 H H
gem-CH2=CClBr 500 H H
gem-CF2=CClBr 470 F F
cis-CFCl=CBrF 470 F F
trans-CFCl=CBrlF 470 F F
Heteronuclear AX Systems
Structure A-nucleus X-nucleus

CHCl2F H F
gem-CHF=CCl2 H F
cis-CHCl=CClF H F
trans-CHCl=CClF H F
CHCl2P(O)Cl2 H P
PCl2F F P
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Two-Spin Systems
500 MHz 1H NMR Spectrum of 2,3-Dibromothiophene

- A Homonuclear AX System with Very Low AB Character
1
2,3-Dibromothiophene was studied quite frequently giving rise to second order H NMR spectra of
AB type when studied at lower frequencies (60 to 100 MHz). But at 500 MHz an AX system is
observed as shown below.:
8
8
5
5
3
3
3
3
7.70 7.65 7.60 7.55 7.50 7.45 7.40 7.35 7.30 7.25 7.20 7.15 7.10 7.05
( ppm)
8
8
5
5
3
3
3
3
7.70 7.65 7.60 7.55 7.50 7.45 7.40 7.35 7.30 7.25 7.20 7.15 7.10 7.05
( ppm)
1
Figure 12 : 500 MHz H NMR of 9.5 mg of 2,3-dibromothiophene in 0.5 ml of CDCl3 (upper spectrum)
and of CD3COCD3 (lower spectrum). Reference: internal TMS.
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Two-Spin Systems
Numerical results for example 1 and example 2 are shown in the following table:
Example 1 Example 2
CDCl3 CD3COCD3
νa Hz 3827.94 3833.31
1
νa Hz 3833.16 3827.54
2
νx Hz 3534.59 3539.99
1
νx Hz 3528.82 3534.22
2
νA Hz 3825.05 3850.43
νX Hz 3531.70 3537.11
∆ν Hz 293.35 313.32
JAX Hz 5.77 5.77
r 50.8 54.3
Inspection of the intensities shows, that the intensity rule given above
[9 ] Ia= Ia= Ix= Ix

1 2 1 2
is not strictly fulfilled in spectra of examples 1 and 2. Only restricted symmetry holds:
[1 0] Ia  Ia
1 2
Ix  Ix
2 1
=Ia Ix=
1
Ia Ix2 2 1
which is an indicator for second order AB systems. The 500 MHz spectrum of 2,3-dibromo-
thiophene will be described as AX system with minute AB character. The analysis of AB spectra
will be discussed in details within the next chapter of this manuscript. But we don’t need to do the
full AB analysis for the 500 MHz spectrum of 2,3-dibromothiophene. The r-value which
characterizes the spectral type is above 50, which justifies the AX approximation for both spectra of
example 1 and example 2 as well.
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Two-Spin Systems
6.1.1 Evaluation of AX Doublets with Broad Lines (Low JAX/HWB Relation)
Consider an arbitrary AX case. The A-doublet is centered at a resonance frequency ν0 and split by
a coupling constant JAX. The spectrum is governed by the spectral half width HWB which is, in this
simplified description, an inverse function of the relaxation time T2:
1
[11] HWB =
πT2
The Lorentzian line shape of a doublet is described by:
1 1
=
[12]
Int(ν ) c [ + ]
1+ b (a − ν ) 1+ b ( −a − ν )2
2 2 2
1 1
=
[13]
Int(ν ) c [ + ]
1+ b (a − ν ) 1+ b (a + ν )2
2 2 2
using constants:
JAX 2 1
[14] a= b= = 2 π T2 =c = T2
2 HWB π HWB
Minima for this function are found for ν = 0 and ν = ± ∞. But where are the maxima of this doublet
function? Since it is tedious to solve this problem (a bi-quadratic equation) algebraically at this
stage a numerical solution is preferred.
A theoretical spectrum is simulated for the A part of an AX spectrum at a resonance frequency of
νA = 0.0 Hz using a coupling constant JAX = 1.0 Hz and HWB set to 0.75 Hz. 128 K data points
span a spectral window ranging from νmax = +5.0 Hz to νmin = -5.0 Hz.
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Two-Spin Systems
Three significant points are observed in the Lorentzian curve: two relative maxima at P1 and P3 and
one relative minimum at P2.
1 3
4 3 2 1 0 -1 -2 -3 -4
(Hz)
Figure 13 : Extrema P1, P2, and P3 in Lorentzian absorption curve.
What can we extract from this Lorentzian curve?
The center νC of P1 and P3 is given by
ν +ν
[15] νC =1 3
2
which is equal to ν2 from P2 and equal to the resonance frequency ν A.
The distance ∆ν between P1 and P3
[16] ∆ ν = ν1 − ν3
is smaller or - in the best case of narrow lines - almost equal to the (absolute value of the) coupling
constant JAX.
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Two-Spin Systems
By Peak Picking the spectrum given above we find a separation of 0.96 Hz.
+0.48 -0.48
4 3 2 1 0 -1 -2 -3 -4
(Hz)
Figure 14 : Extrema P1 and P3 by Peak Picking in Lorentzian absorption curve.
Using the tool Multiplet from TopSpin leads to a splitting of 0.9776 Hz, but repeating the Multiplet
procedure on this same spectrum yields a separation of 0.9656 Hz.
So bear in mind: Results from Multiplet depend on the operator´s ocular and manual
precision.
The tool Deconvolution in TopSpin may be used to separate the individual components of super-
imposed Lorentzian lines:
4 3 2 1 0 -1 -2 -3 -4
(Hz)
Figure 15 : Deconvolution of the Lorentzian absorption curve.
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Two-Spin Systems
Results are listed in the following Deconvolution Table:
No. Position Intensity Width Integral

[Hz] (abs.) [Hz] (abs.)
1 +0.48 955 0.79 1.239368e+007
2 -0.48 955 0.79 1.239368e+007
Deconvolution Table of the Lorentzian Absorption Curve
Red and green are marked components, black the corresponding superposition of those
components, while blue is the primary simulated curve. Obviously the deconvolution is not fully
optimized
Auxiliary Graphical Plots to Analyze a Broadened Lorentzian Doublet
Consider an AX system with νA = 0 Hz and JAX = 1 Hz. A series of simulations varying spectral half
width HWB yields two functions:
a) the apparent separation ∆ν of peaks P1 and P3 as defined in [16]

b) the relative intensity ratio Ir at midpoint frequency as defined in [17]
I2
[17] Ir =
I1 + I3
1,2
1
0,8
0,6
0,4
0,2
0
-0,2
0 0,5 1 1,5 2
Figure 16 : Auxiliary graphical plots to analyze a broadened Lorentzian doublet. x-axis: Spectral half
width HWB. y-axis: Separation of peak maxima ∆ν . y-axis: Relative intensity ratio Ir.
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Two-Spin Systems
Limiting Situations:
if then
both doublet lines are well separated and the peak maxima
HWB < 0.1 |JAX|
represent the effective Larmor frequencies νa1 and νa2 resp..
HWB > 1.75 |JAX| a broad singlet is seen instead of a doublet.
It is interesting and useful to know more about the algebraic solution of the doublet problem.
A-Doublet of AX System
Simulate the A part of an AX system with νA = 0 Hz, JAX 1 Hz, HWBA = 1 Hz and observe the
typically broadened doublet.
1 3
4 2 0 -2 -4
(Hz)
Figure 17 : The A part of an AX system with νA = 0 Hz, JAX = 1 Hz, HWBA = 1 Hz.
The apparent doublet separation s = ν(P1)-ν(P3) is definitely smaller than JAX. By Peak Picking we
find s = 0.92 Hz while Multiplet Analysis yields s = 0.9145 Hz. The algebraic absolute value of the
coupling constant JAX can be calculated by the following expression:
JAX J2AX J2AX

= [18]
s HWB 2 ( + 1) − ( + 1)
HWB HWB2 HWB2
which is found by differentiating the reduced Lorentzian function as shown below.
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Two-Spin Systems
Differentiating the Reduced Lorentzian Function
Using
JAX
[19] a=
HWB
ν
[20] x=2
HWB
the reduced Lorentzian line shape for the A-doublet of an AX system follows:
1 1
=
[21]
L +
1+ (a − x)2 1 + (a + x)2
The first derivative is given by:
dL 4 x [x 4 + 2 x 2 (a2 + 1) − (a2 + 1)(3 a2 − 1)]

[22] =
dx [1+ (a − x)2 ]2 [1+ (a + x)2 ]2
The first two minima are found for the spectral boarders:
[23] x=±∝
The third minimum follows from:
[24]
4 x [x 4 + 2 x 2 (a2 + 1) − (a2 + 1)(3 a2 − 1)] =
0
at the center of the doublet
[25] x =0
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Two-Spin Systems
Two maxima symmetrically placed around the spectral center are derived from:
[26] x=
± 2 a ( a2 + 1) − ( a2 + 1)
The reduced peak separation sx is given by:
[27]=sx 2 2a (a2 + 1) − (a2 + 1)
The test case shown above used JAX = 1 Hz and HWB = 1 Hz, hence a = 1, x = ±0.9102, and
ν = ±0.4551 Hz. By peak picking the spectrum we find ν = ±0.46 Hz. Peak separation s = 0.92 Hz.
A limiting value of a is derived:
1
[28] =
a = 0.57735.....
3
governing the apparent spectral pattern:
if a < 0.57735 The A part appears as a broadened singlet

if a > 0.57735 The A part appears as a doublet
Expanded Equations
Maxima in the A-doublet of the AX system are found at
HWB JAX J2AX J2AX

[29] ν = ν0 ± 2 ( + 1) − ( + 1)
2 HWB HWB2 HWB2
The doublet separation s is given by
JAX J2AX J2AX

[30] s HWB 2 ( + 1) − ( + 1)
HWB HWB2 HWB2
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Two-Spin Systems
If we know HWB, or make an educated guess of HWB, we can calculate the missing coupling
constants JAX from the parameter s as deduced from the experimental spectrum. The easy way to
JAX is deconvolution of the experimental spectrum with TopSpin.
Using
JAX
[31] a=
HWB
s
[32] x=
HWB
We can simulate the auxiliary function
[33] x=
± 2 a ( a2 + 1) − ( a2 + 1)
This auxiliary function x = f(a) is simulated and shown in the plot below:
Figure 18 : Simulation of the auxiliary function x = f(a).
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Two-Spin Systems
This helps to classify the doublet evaluation:
If then
a>2 the doublet splitting approximates JAX sufficiently
0.57735 < a < 2 a correction is required
a < 0.57735 a singlet is seen, the doublet splitting is not resolved
6.1.2 Some Examples for Homonuclear AX Spin Systems
Dichloroacetaldehyde and Dichloroacetaldehyde Diethyl Acetal
Cl Cl OEt
HA
C C HX HA C C HX
O
Cl Cl OEt
δA ppm 9.79 5.62
δX ppm 6.04 4.64

JAX Hz 2.9 5.6
1
Spin assignment by comparison with H NMR spectra of acetaldehyde, acetaldehyde diethyl acetal
[δH(CH) = 4.7 ppm] and 1,2-dichloroethane (δH(CH) = 5.9 ppm] led to
Cl OEt EtO Cl
HA C C HX HA C C HX
Cl OEt and not to EtO Cl
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Two-Spin Systems
1
Simulation of 500 MHz H NMR Spectra for Dichloroacetaldehyde and Dichloroacetaldehyde
Diethyl Acetal
4904 4900 4896 4892 4888 3028 3024 3020 3016 3012
(Hz) (Hz)
Figure 19 : Dichloroacetaldehyde. A part (left). X part (right).
2816 2812 2808 2804 2328 2324 2320 2316 2312

(Hz) (Hz)
Figure 20 : Dichloroacetaldehyde diethyl acetal. A part (left). X part (right).
For details read: G. J. Karabatsos; D. J. Fenoglio, S. S. Lande; J. Amer. Chem. Soc. 91, 3572-
3577 (1969). Compare with: G. J. Karabatsos; D. J. Fenoglio; J. Amer. Chem. Soc. 91, 1124-1129
(1969). Y. Fujiwara, S. Fujiwara; Bull. Chem. Soc. Japan, 36, 574-578 (1963). Y. Fujiwara, S.
Fujiwara; Bull. Chem. Soc. Japan, 36, 1106-1109 (1963).
6.1.3 A Heteronuclear AX Spin System with Rotational Isomerism
P. Finocchiaro, Catania, synthesized N-acetyl-amino-1-phenyl-methanephosphonicacid, a

31 1 1
substituted phospha-analogue of glycine. 81 MHz P{ H } and 200 MHz H NMR spectra were
taken from solutions in CDCl3 (with one drop of CD3OD / 0.5 ml in NMR tube).
By proton decoupling two phosphorus singlets were found at 21.1983 ppm (52%) and 19.5590 ppm
(42%).
The phosphorus coupled H NMR yielded two sharp doublets for the CHP protons at δH 6.0252
1
2 2
ppm (59%, JPH = -9.24 Hz) and 5.6331 ppm (41%, JPH = -9.58 Hz), each representing the A part of
an AX system.
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Two-Spin Systems
5
The CH3CO resonated as slightly broadened doublets at 1.8845 ppm (41%, JPH=3.0 Hz) and
5
1.8510 ppm (59%, JPH=3.6 Hz), caused by A3 parts of A3X system.
These observations indicate rotational isomerism like:
Ph Ph
lp Ph
H 3C N Ph H 3C N+ Ph O- N+ Ph
C C C C C C
O H PO3H2 O- H PO3H2 CH3 H PO3H2
1
Please pay attention: the H integrals for CHP and CH3CO protons indicated consistently a ratio
31 1
59:41 for the pair of rotamers while the routine P{ H} integrals yielded a ratio of 52:48.
Hence optimize the settings of your NMR spectrometer for good integrals of (proton
decoupled) hetero nuclei.
Inspect the following spectra:
31 1
Figure 21 : P{ H} – X part of X1.
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Two-Spin Systems
1
Figure 22 : H spectral part for CHP – A part of AX.
1
Figure 23 : H spectral part for CH3CO – A3 part of A3X.
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Two-Spin Systems
6.1.4 The AX Spin System in a Mono Fluorinated Cynnamic Acid C9H7O2F
1
A heteronuclear AX spin system is detected in a 400 MHz H NMR spectrum of a mono fluorinated
1
cynnamic acid C9H7O2F. Inspect the 300 MHz H NMR spectrum shown below:
1
Figure 24 : 300 MHz H NMR spectrum of a monofluorinated cynnamic acid.
The characteristic resonances of the phenyl unit C6H5 are found between 8.1 and 7.7 ppm (and will
be discussed in details in the chapter on 5-spin systems of this manuscript). In addition the doublet
of an olefinic proton is found between 7.45 and 7.3 ppm.
Hence this mono-fluorinated cynnamic acid C9H7O2F does not hold an ortho-, meta- or para-
fluorophenyl C6H4F-group bound to a -CH=CH-COOH skeleton. Fluorine is situated in the olefinic
part.
Four alternative structures are expected for C6H5-CH=CF-COOH and C6H5-CF=CH-COOH resp.:
F H COOH COOH
H C F C H C F C
C COOH C COOH C F C H
H H H H H H H H
1 2 3 4
H H H H H H H H
H H H H
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Two-Spin Systems
The proton and fluorine spins in the -CH=CF- skeletons from each of the four models shown above
represent a heteronuclear AX spin system with structure specific parameters δH, JFH and δF. For
3
our studies here only the 300 MHz H NMR spectrum is available yielding δH = 7.3664 ppm and
1
3
JFH = 35.77 Hz as obtained by Peak Picking with TopSpin.
Figure 25 : Peak picking the A part of AX in the olefinic region.
In addition TopSpin provides another convenient tool Multiplet:
Figure 26 : Multiplet analyzes the A part of AX in the olefinic region.
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Two-Spin Systems
which needs some manual experience to place the markers of Multiplet correctly as can be seen in
the next two figures:
Figure 27 : Multiplet Analysis : SHIFT (δH ) = 7.3715 ppm. J = 35.6651 Hz.
Figure 28 : Multiplet Analysis : SHIFT (δH ) = 7.3714 ppm. J = 35.7722 Hz.
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Two-Spin Systems
TopSpin provides a very useful tool with Deconvolution for spectral analysis. The doublet region
yields the following graphic and data: δH = 7.3715 ppm, νH = 2949.645 Hz, JFH = 35.77 Hz, as
shown below:
Figure 29 : Deconvolution analysis. Lower: experimental. Middle: simulated after deconvolution. Upper:
difference spectrum (intensity expanded by a factor of 10).
Numerical Results from Deconvolution:
Shift Frequency HWB HWB Intensity Area

[ppm] [Hz] [ppm] [Hz]
7.416 2967.53 0.00270 1.082 6.819 63.014
7.327 2931.76 0.00270 1.080 6.833 63.062
3
After comparing the vicinal coupling constants JFH from difluoroethylenes:
F F F H F H
H H H F F H
3 3 3
JFH(trans) = 72 Hz JFH(cis) = 4.4 Hz JFH(cis) = 0.7 Hz
3
JFH(trans) = 33.0 H
we may conclude: the trans-structures of isomers 3 and 4 are favored.
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Two-Spin Systems
So for the time being, we are not able to assign unequivocally one of both structures trans-C6H5-
CH=CF-COOH (3) or trans-C6H5-CF=CH-COOH (4) to this sample of fluorocynnamic acid.
1
Some attempts to advance structural analysis were made: The left line of the olefinic H doublet
was subjected to selective deconvolution in order to study the experimental line shape:
Figure 30 : Lower: experimental spectrum; middle: simulated spectrum using data from Lorentzian
deconvolution; upper: difference spectrum.
Fit Shift Frequency HWB HWB Intensity Area

Lorentzian 7.327 2931.76 0.00271 1.084 6.829 63.226
Gaussian 7.327 2931.75 0.00335 1.342 6.290 48.882
A spectral half width of 1.08 Hz for those doublet lines characterizes broadening. Obviously the
simple AX model does not completely fit the experimental line shape, neither by Lorentzian nor by
Gaussian shape. This might be due to non-resolved overlapping long range coupling constants, e.
n
g. of type JHH (n=4-6) between the olefinic –CH= and aromatic C6H5 protons. We will discuss this
1
phenomenon when looking into the H NMR spectrum of styrene, an 8-spin problem, at an
advanced level of this manuscript. But it might be useful to give a brief report of those studies at
this state of the manuscript.
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The total 400 MHz spectrum of fluorocynnamic acid was iterated as [AB]2CDX system to yield the
following fit:
1
Figure 31 : Experimental (lower) and iterated (upper) H NMR spectrum of fluorocynnamic acid.
Indeed two couplings between olefinic and aromatic protons (0.46 Hz and 0.36 HZ) were found
including a long range coupling JFH of 0.29 Hz between the “olefinic“ fluorine and the ortho protons
of the C6H5 unit. This supports model 3 for C6H5-CH=CF-COOH. NMR data listed below, using the
spin enumeration:
H2
H6 COOH
H4 C C C
C C F7
C C
H5 C H1
H3
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NMR Data of Fluorocynnamic Acid
Spin No. Isovalue Frequency [Hz] HWB [Hz] Shift [ppm]

1 1 3228.7475 0.4642 8.0691
2 1 3228.7475 0.4642 8.0691
3 1 3123.5719 0.5732 7.8063
4 1 3123.5719 0.5732 7.8063
5 1 3108.5830 0.5802 7.7688
6 1 2949.5851 0.4773 7.3715
7 19 arbit. def. - -
n
i k Jik [Hz] n Type Type
1 2 1.9300 4 meta HH
1 3 7.9000 3 ortho HH
1 4 0.5531 5 para HH
1 5 1.2272 4 meta HH
1 6 0.4572 4 l.r. HH
1 7 0.2931 5 l.r. FH
2 3 0.5531 5 para HH
2 4 7.9000 3 ortho HH
2 5 1.2272 4 meta HH
2 6 0.4572 4 l.r. HH
2 7 0.2931 5 l.r. FH
3 4 1.4350 4 meta HH
3 5 7.4897 3 ortho HH
3 6 0.3570 5 l.r. HH
3 7 0.0000 6 l.r. FH
4 5 7.4897 3 ortho HH
4 6 0.3570 5 l.r. HH
4 7 0.0000 6 l.r. FH
5 6 0.0000 6 l.r. HH
5 7 0.0000 7 l.r FH
6 7 35.7716 3 l.r. FH
l. r. = “long range” coupling constants
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The Deuterated Solvent
Unfortunately this sample of fluorocynnamic acid did not contain TMS as an internal or external
reference. The list of acquisition parameters is not complete. But we detect the spectral pattern
characteristic for CHD2-X at δH = 2.401 ppm exhibiting a coupling of 2JDH = 2.2 Hz. In addition
weaker signals are found at δH = 2.417 ppm from CH2D-X and at δH = 2.434 ppm from CH3-X units
Those data were obtained by Deconvolution:
1
Figure 32 : Deconvolution of the residual H NMR peaks from deuterated solvent.
Corresponding numerical results are shown in the next table:
Shift Frequency Width Width Intensity Area

2.434 973.81 0.00115 0.460 0.389 1.530
2.423 969.45 0.00165 0.662 1.845 10.432
2.417 967.27 0.00158 0.633 1.860 10.053
2.412 965.04 0.00143 0.574 7.492 36.743
2.406 962.82 0.00141 0.564 11.003 53.033
2.401 960.62 0.00145 0.580 15.393 76.303
2.395 958.41 0.00142 0.569 9.791 47.631
2.390 956.21 0.00137 0.548 4.596 21.526
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Common solvents with deuterated methyl groups are listed below together with chemical shifts
expected for the residual peaks and corresponding coupling constants.
δH [ppm]
2
Solvent JDH [Hz]
CD3-CN 1.93-1.94 2.5
CD3-COOD 2.00-2.04 2.2
CD3-CO-CD3 2.04-2.09 2.2
CD3-C6D5 2.09-2.30 2.3
CD3-SO-CD3 2.49-2.50 1.7-1.9
[(CD3)2N]3PO 2.52 2.0
2.73-275 1.9-2.0
(CD3)2NCOD
2.91-2.92 1.9-2.0
CD3-OD 3.30-3.39 1.7-1.9
CD3-NO2 4.30-4.33 2.0
Regarding the chemicals shift, this unknown solvent might be dimethylsulfoxide-d6. But the
2
coupling constant JDH is more consistent with acetone-d6. In both cases, the chemical shift should
be adjusted to the residual peak of the solvent used.
We have solved the spectral pattern regarding coupling constants and determined accurately the
differences in resonance frequencies and chemical shifts between those protons. But we do not
know the accurate resonance frequencies νH and chemicals shifts δH.

Here we meet the second riddle of this example. So, please, bear in mind: a reference compound
in your sample and a complete protocol are requested for good NMR spectra. The number
of data points per half width should be around 15. The digital resolution in this spectrum is
rather low, as can be seen in spectra shown above.
6.1.5 CHF=CHP(O)(OCH3)2 – a Heteronuclear RX System
Dehydrofluorination of CHF2-CH2-P(O)(OCH3)2 leads to a genuine mixture of cis- and trans-isomers

of CHF=CHP(O)(OCH3)2. The individual isomers are identified by specific NMR parameters.
Decoupling the protons A and M in AMRX simplifies the spectrum to a heteronuclear RX system
19 31 3 3
consisting of F and P spins yielding the stereo specific coupling constants JPF(cis) < JPF(trans).
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19
An analogous pattern would be observed in the F NMR spectrum (the R part).
H H F H
C C C C
F P(O)(OCH3)2 H P(O)(OCH3)2
δP νP
3
Isomer JPF
[ppm] [Hz] [Hz]
cis 11.23 910.0 13.54
trans 15.56 1260.0 73.88
P NMR measured at 81 MHz, δP [ppm] and νP [Hz] vs. ext. 85%

31
Protons decoupled at 200 MHz.
H3PO4.
13
6.1.6 C-Enriched Molecules – the Observation of JCC and JNC in AX Type
Spectra.
13 1 13 13
The proton decoupled C{ H} NMR spectrum of Br CH2- COOEt
13 13
Br C C O Et
H O
shows the A and X parts of an AX system with two signals at 167 ppm and 26 ppm, each split with
1 13
JCC = 67 Hz. (Additional remark: Bromine causes upfield shifts of 5 ppm ( CH2) and 4 ppm
13
( CO) in comparison to the parent compound CH3COOEt). (Solvent: CDCl3).
15 1 15 13 15
A proton decoupled N{ H} NMR spectrum of Boc- NH- CH2-COOH (Boc-[ N]-glycine) exhibits
two separate signals for the A parts of two individual AX systems.
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Two-Spin Systems
Two individual E/Z conformers are formed:
CH3 H H CH3 O H H
15 13 15 13
CH3 C O C N C COOH CH3 C O C N C COOH
CH3 O H CH3 H
δN (15N)
1
Conformer JNC
[ppm] [Hz]
E major 75.5 14
Z minor 79.5 12
13 1 15 13
The proton decoupled C{ H} NMR spectrum of Boc2 NH with natural carbon (not C enriched)
shows a neat A-doublet from a single AX system. What did you expect?
CH3 H CH3
15
CH3 C O C N C O C CH3
CH3 O O CH3
For details about examples shown above see: L. Grehn, U. Ragnarsson, and C. J. Welch; J.
Chem. Educ. 74, 1477- 1479 (1997).
Application of 13C and 15N Nuclei to Study the Protolytic Equilibrium of HCN - CN-
-
The weak acid HCN and the corresponding anion base CN are subject to a protolytic equilibrium.
1 13 15 13 15 -
The coupling constants JNC, visible as JAX in the AX-doublets of H C N and C N , are
indicative for the protolytic state:
1
JNC
13 15
H C N 19 Hz
13 15 -
C N 6 Hz
13 15 13 15
Stepwise titration of K C N vs. HCl in connection with C- and N NMR lead to pH-dependent
1
JNC parameters.
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Two-Spin Systems
A corresponding plot is shown below:
13 15 1
Figure 33 : Stepwise titration of K C N vs. HCl. JNC depends on pH.
This example was extracted from private communication with R. E. Wasilishen, Canada. NMR-
controlled titrations will be discussed in one of the following chapters of this manuscript.
6.2 The AB System – Spin System No. 3
1 2
AB r ≈ 1
The most simple second order spectrum is characterized by |rAB| ~ 1 and consists – like the first
order system AX - of four resonance lines (frequencies: ν1, ν2, ν3, ν4; intensities: I1, I2, I3, I4,), which
are arranged symmetrically around the spectral center νC = ½ (ν A + ν B ). The characteristic

separation JAB is found twice - like JAX in the AX case. But in contrast hereto the midpoints of the A-
or B-line pairs do not represent the resonance frequencies νA or νB resp.. A so called “roof effect”
is observed, where the stronger intensities are affiliated with the inner lines, and the weaker with
the outer lines. The sign of JAB does not influence the spectral pattern.
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Two-Spin Systems
Figure 34 : A typical AB spectrum
For the analysis of the AB spectral pattern the following definitions will be used:
[1] so = ν1 - ν 4 =C+JAB Separation of outer lines
[2] si = ν 2 - ν3 =C - JAB Separation of inner lines
[3] C= ν1 - ν3 = ν 2 - ν 4 Repeated spacing C
[4] ∆ = ν A - νB Difference of resonance frequencies
Suitable equations to analyze the AB spectrum are given below. Use a ruler to check your
experimental spectrum.
Frequencies:
1 1 1 1
[5] ν C= (ν A + νB=) (ν1 + ν 4=) (ν 2 + ν 3=) (ν1 + ν 2 + ν 3 + ν 4 )
2 2 2 4
1 1
[6] JAB = (so − si ) = (ν1 − ν 2 ) = (ν 3 − ν 4 ) = (ν1 − ν 2 + ν 3 − ν 4 )
2 2
[7] =
∆ so ⋅ si The absolute value of ∆ is obtained
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Two-Spin Systems
1
[8] ν A =ν C + ∆ νA > νB by definition
2
1
[9] νB =ν C − ∆ νA > νB by definition
2
[10] C = ∆ 2 + J2AB
∆
[11] rAB =
JAB
Intensities:
[12] Io = I1= I4 Intensity of outer lines
[13] Ii= I2= I3 Intensity of inner lines
[14] Ii :Io = so :si

[15] Ii + Io =
2
Hence
2so
[16] Ii =
si + so
2si
[17] Io =
si + so
On the following pages you will find some examples of AB spectra from 2,4-dibromothiophene.
Please analyze and simulate those spectra using equations given above.
Br H
C C
H C C Br
S
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Two-Spin Systems
ν1 = 690.06 JAB =
ν2 = 688.48 νC =
ν3 = 687.52 ∆ν =
ν4 = 685.92 νA =
νB =
so = δA =
si =
δB =
C=
6 .9 6 6 .9 2 6 .8 8 6 .8 4 6 .8 0
rAB =
(p p m )
Figure 35 : 100 MHz AB spectrum of 2,4-Dibromothiophene. Insert your own results.
Observe the strong “roof effect” which indicates strong coupling. Use the results obtained above
1
from 100 MHz analysis, simulate 200 MHz and 500 MHz H NMR spectra and compare the
decrease of second order character in this series.
200 MHz 500 MHz

νA 1378.0 3445.0 Hz
νB 1374.0 3435.0 Hz
JAB 1.6 1.6 Hz
rAB 2.5 6.25
Transition frequencies and intensities for the AB system can be calculated algebraically by:
[18] ∆ = ν A − νB
1
[19] ν C= ( ν A + νB )
2
1
[20] ν1 =ν C + ( ∆ + JAB )
2
1
[21] ν 2 = νC + ( ∆ − JAB )
2
1
[22] ν3 = νC − (∆ − JAB )
2
1
[23] ν 4 = νC − ( ∆ + JAB )
2
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Two-Spin Systems
∆ − JAB
[24] Io = I1= I4 =
∆
∆ + JAB
[25] Ii= I2= I3=
∆
6.2.1 2,3-Dibromothiophene – a Typical Example for AB Spectra
The protons from 2,4-dibromothiophene show a slightly weaker coupling than those from
2,3-dibromothiophene:
H Br
C C
H C C Br
S
A simulated 100 MHz AB spectrum of 2,3-dibromothiophene is given below:
Figure 36 : 100 MHz AB spectrum of 2,3-dibromothiophene
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Two-Spin Systems
Analyze the 100 MHz NMR spectrum and simulate 200 MHz and 500 MHz spectra using
parameters:
δA 7.06 ppm
δB 6.87 ppm
JAB 5.7 Hz
rAB 3.3 Hz
6.2.2 Geometrical Solution of the AB Problem
Combining the equations shown above and the Pythagorean rule leads to a simple solution for the
AB analysis. Just scales and ruler are required.
The difference of resonance frequencies ∆ is obtained according to the following figure.
Figure 37 : Geometric solution using Pythagoras
Make a circle around P1 with radius C = ν 1 - ν 3 . This circle will hit the intensity line of I2 in P5. The
distance P2 - P5 in units of the frequency scale is equal to ∆.
Generalization of the AB Case
It is easy to show, that the AB case has two limiting cases depending on the spectral relation r:
|r| Spin System In Practice Remarks

|r| » 1 AX |r| > 50. See chapter above on AX.
|r| « 1 A2 |r| < 0.02. Limit ∆ = 0. See chapter below on A2.
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6.2.3 Further Practical Examples of AB Systems are Shown Below
Consider the stereo isomers of phenyldichloropropionicacid. Three isomers (1 to 3) have geminal

2
methylene protons with coupling constants JHH while two isomers (4 and 5) have vicinal protons
3
with coupling constants JHH:
H Ph H Cl Cl H
Cl C C* COOH Ph C C COOH Ph C C COOH
H Cl H Cl Cl H
1 AB 2 A2 3 A2
H H H H
Cl C C* COOH Cl C* C* COOH
Cl Ph Ph Cl
4 AB 5 AB
Geminal protons: Carbon C1 in 1 is a chiral center; hence the geminal protons attached to C2 are
diastereotopic and anisochronous forming an AB system. 1 exists in RC and SC stereo isomers
which in isotropic solvents will have identical NMR parameters. Optically active solvents will induce
solvation diastereomers with individual NMR data.
Carbon C1 in 2 and carbon C2 in 3 are prochiral centers, where the geminal protons attached to C2
in 2 and C1 in 3 are enantiotopic and isochronous in A2 systems.
Vicinal protons: Protons attached to C1 and C2 in compounds 4 and 5 are non-isochronous and
form AB systems. Carbon C1 in 4 is a chiral center, hence 4 exists in RC and SC stereo isomers
which in isotropic solvents will have identical NMR parameters. Optically active solvents will give
rise to solvation diastereomers with individual NMR data (see above). Carbons C1 and C2 in 5 both
are chiral centers, existing in RC or SC configurations. 5 gives rise to threo and erythro forms with
distinct AB systems in isotropic solution.
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6.2.4 Sterically Hindered Ethanes CHRBr-CHR´Br
H H
R C C R´
Br Br
Parameter Type Case 1 Case 2 a Case 2 b

R C6H5 C6H5 C6H5
R´ C(O)C6H5 C(O)OC2H5 C(O)OC2H5
Solvent CDCl3 CDCl3 CD3-SO-CD3
δ1 δH 5.82 5.30 5.65 ppm
δ2 δH 5.65 4.78 5.55 ppm
ν1 νH 349.2 318.0 339.0 Hz
ν2 νH 339.9 286.8 333.0 Hz

3
J12 JHH 10.3 12.0 12.0 Hz
r12 0.9 2.6 0.5
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Using those parameters the following 60 MHz spectra were simulated:
6.0 5.8 5.6 5.4 5.2 5.0 4.8 4.6
6.0 5.8 5.6 5.4 5.2 5.0 4.8 4.6
6.0 5.8 5.6 5.4 5.2 5.0 4.8 4.6

(ppm)
Figure 38 :
1
60 MHz H NMR spectra for cases 1 and 2. upper: 1; middle 2a, lower: 2b. δH and νH vs.
internal TMS.
For references see:

Case 1: E. W. Garbisch Jr.; J. Chem. Ed. 45, 311-321 (1968).
Case 2: J. E. Gurst, C. M. Dellinger, J. Jacobus; J. Chem. Ed. 62, 871-873 (1985).
Simulate 200 MHz and 500 MHz spectra with TopSpin and observe spectral order.
The canonical rotamers for compounds of type CHRBr-CHR´Br are shown below:
R R R
Br H2 H2 R´ R´ Br
H1 Br H1 Br H1 Br
R´ Br H2
I II III
Figure 39 : AB Systems in rotamers of cases 1 and 2
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Two-Spin Systems
3
The spectral patterns of 1, 2a and 2b reveal large vicinal coupling constants JHH indicating the
3
dominance of rotamer I forms. JHH depends on the dihedral angle H-C-C-H.
3 3
Essentially: JHH (trans) > JHH (cis). This behavior, described by KARPLUS type functions, will be
discussed in more details in subsequent chapters on 3-spin cases.
Bear in mind: solvation effects influence the chemical shifts of protons δH and coupling constants
3
JHH considerably. Hence specify solvent type, concentration and temperature of your sample
in your protocols.
6.2.5 The CH2 Group in the Racemic Form of a Cyclo-Propane Derivative
H3 C CH3
HA
(H3C)3SiO OSi(CH3)3
HB
gives rise to an AB spectrum with data shown in the list below.
Group Param.
CH2 δH(A) 0.25 [ppm]
CH2 δH(B) 0.76 [ppm]
CH2 JAB (-)6.5 [Hz]
CH3 δH (CH3) 1.28 [ppm]
(Solvent: CCl4. δH [ppm] vs. TMS). 60 MHz H NMR.

1
In this particular cyclopropane derivative methylene protons do not couple with methyl protons,
4
hence JHH = 0.
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Two-Spin Systems
1.4 1.2 1.0 0.8 0.6 0.4 0.2

1
Figure 40 : 100 MHz H NMR simulation.
At 500 MHz the methylene protons will form an AX system.
Please bear in mind: The methyl singlet is situated to the left of the methylene singlet for this
cyclopropane compound. The reverse order is valid for CH3-CH2-functions in most of the ethyl
3
compounds (and methyl and methylene groups are coupled by JHH).
For details see:
R. Le Goaller, J.-L. P. Arnaud and P. Arnaud; Org. Magn. Res. 1, 337-340 (1959).
6.2.6 AB Spectra with Nucleus Specific Half Widths
The following derivatives of thiazol shown below give rise to AX or AB spectra.
H COOH H H
C C C C
N S N S
C C
H Br
AX AB
Particular attention was drawn towards 2-bromothiazol (N. C. Pyper and R. K. Harris; Mol. Phys.
20, 467-480 (1970).
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Two-Spin Systems
Nuclear specific half widths (HWB) were observed, which depend on type of solvent, concentration
and temperature. Four typical cases are listed below:
Spect. Temp. ∆ν(AB) T2(A) T2(B) HWB(A) HWB(B) JAB rAB

°C [Hz] [sec] [sec] [Hz] [Hz] [Hz]
1 33.5 18.74 0.464 3.88 0.686 0.082 3.56 5.26
2 70.0 19.82 0.286 2.36 1.113 0.135 3.56 5.57
3 32.0 2.97 0.490 0.994 0.650 0.490 3.56 0.83
4 68.0 7.16 0.270 0.761 1.179 0.270 3.56 2.01
Sample 1 for Spectra 1 and 2:

93 mol % 2-bromothiazol, 3 mol % cyclohexane, 3 mol % TMS.
Sample 2 for Spectra 3 and 4:

19 mol % 2-bromothiazol, 63 mol % 2,6-dimethyl-cyclohexanone, 14 mol % CCl4,
32 mol % dioxane, 2 mol % TMS. The magnetic field was locked to TMS.
5 0 -5
(Hz)
Figure 41 : Simulation of spectrum no. 4. Spectrum centered at 0 Hz. Four peaks at 5.77 Hz, 2.22 Hz, -
2.23 Hz, -7.78 Hz.
3
All AB spectra were centered arbitrarily around zero. A uniform coupling constant JHH of
3.56 +/- 0.05 Hz was observed in spectra 1-4. The high frequency proton A, affiliated with broader
lines, is attributed to H-C=N, the low frequency proton B, connected with sharper lines, to H-C-S.
100 MHz spectra were taken. Comparison with 60 MHz spectra showed, that in this case the
spectral half widths of lines are field dependent. This line width effect is governed by a
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Two-Spin Systems
2 14
nitrogen-proton coupling JNH and the nitrogen relaxation rate T1( N). Hence the spectra shown
2 2 3 1
above are proton parts of total A B X systems, where A and B stand for spins I( H) = 1/2 and X for
14
I( N) = 1.
2 2
A B
H H
C C
3
X N S
C
Br
For details see the paper of PYPER and HARRIS quoted above. Spectra from spins I > ½ will be
discussed in separate chapters of this manuscript.
6.3 The A2 System – Spin System No. 4
1 2
A2 r=0
The A2 spectrum consists of a single line centered at ν A . Remember the general rule for the AB
case and show for the limiting case of the AB for ν A = ν B (∆ = 0), that line ν 2 and ν 3 degenerate,
the combined intensity (I2 + I3) is 4. Hence the outer lines ν 1 a n d ν 4 will not be visible having
intensities of zero.
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Two-Spin Systems
Figure 42 : A2 spectrum - arbitrarily centered at νA = 0.
The A2 system is found in many practical examples, e.g.:

a) Aromatic protons in 1,2,3,4- and 1,2,4,5-tetrachlorobenzene,
b) Olefinic protons in cis- and trans-CHCl=CHCl or maleic and fumaric acids,
c) aliphatic protons in geminal CH2 groups like in CH2Cl2,
d) Fluorines in symmetric CF2X2 compounds.
However, the signal of CF2Cl2 is split by isotope shifts into 3 distinct lines for
35 35 37 37
isotopomers CF2 Cl2, CF2 Cl Cl and CF2 Cl2 as discussed above in more
general terms in chapter A1 under CFCl3.
1
Symmetrically substituted tetrachlorobutadienes 1 and 2 give rise to H NMR spectra of A2 type
while asymmetrically substituted cases 3 and 4 yield AX systems when measured at sufficiently
high frequencies, e.g. 270 MHz.
See also the chapter above: The AX System – Spin System No. 2.
δH (A) δH (X)
n
case JHH n type
1 CCl2=CH-CH=CCl2 6.67 n.d. 3 A2
2 (Z,Z) CHCl=CCl-CCl=CHCl 7.35 n.d. 5 A2
3 (E) CCl2=CH-CCl=CHCl 6.70 6.55 1.45 4 AX
4 (Z) CCl2=CH-CCl=CHCl 6.71 6.57 1.15 4 AX
n.d. = not determined.
Read: D. Botta, E. Mantica, L. Castellani, G. Dotelli and L. Zetta; Magn. Res. Chem. 36, 885-891
(1998).
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Two-Spin Systems
The CH2 Group in Trans-1,2-dimethyl-1,2-bis(trimethylsilyloxi)-cyclopropane
H3 C OSi(CH3)3
HA
(H3C)3SiO CH3
HA
gives rise to an A2 singlet centered at 0.51 ppm (Solvent: CCl4. δH [ppm] vs. TMS). The methylene
4
protons do not couple with the methyl protons ( JHH = 0). ´
System Group δH
A2 CH2 0.51 [ppm]
A3 CH3 1.36 [ppm]
1.4 1.2 1.0 0.8 0.6 0.4 0.2

(ppm)
1
Figure 43 : H NMR spectrum of trans-1.2-dimethyl-1,2-bis(trimethylsilyloxi)-cyclopropane showing an
A2 singlet at 0.51 ppm for the CH2 group (and an A3 singlet at 1.26 ppm for the CH3 group).
For details see:

R. Le Goaller, J.-L. P. Arnaud and P. Arnaud; Org. Magn. Res. 1, 337-340 (1959).
Please bear in mind:

The methyl singlet is situated to the left of the methylene singlet for this cyclopropane compound.
The reverse order of chemical shifts δH is valid for CH3-CH2-functions in the majority of ethyl
compounds.
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7 Three-Spin Systems
As shown in the general introduction the absolute value of the spectral relation rik is us e d to
c l as s if y t he ten individual three-spin systems, which will be dealt with in subsequent chapters.
Please remember the definitions:
∆ik
[1] rik =
Jik
[2] ∆ik = νi − νk
The Ten 3-Spin Systems
No. System r12 r13 r23

5 AMX »1 »1 »1 ν1 ≠ ν2 ≠ ν3
6 ABX ∼1 »1 »1 ν1 ≠ ν2 ≠ ν3
7 AXX´ »1 »1 0 ν1 ≠ ν2 = ν3
8 AX2 »1 »1 0 ν1 ≠ ν2 = ν3
9 ABC ∼1 ∼1 ∼1 ν1 ≠ ν2 ≠ ν3
10 ABB´ ∼1 ∼1 0 ν1 ≠ ν2 = ν3
11 AB2 ∼1 ∼1 0 ν1 ≠ ν2 = ν3
12 AAÁ´´ 0 0 0 ν1 = ν2 = ν3
13 AA´2 0 0 0 ν1 = ν2 = ν3
14 A3 0 0 0 ν1 = ν2 = ν3
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8 of those 10 systems are relevant to practical work as shown in the next diagram:
We will study these systems in the following chapters.
7.1 The AMX System – Spin System No. 5
2 3
The AMX spectrum is characterized by a total of 12 lines. In each A, M and X part 4 equi-intense
lines are found, which are symmetrically arranged in two pairs around ν A , ν M and ν X r es p.
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Three-Spin Systems
Figure 44 : A hypothetical AMX spectrum.
The absolute values of coupling constants JAX, JAM and JMX will be directly accessible from line
separations. Each of those three “repeated spacings” is found four times in the total AMX
spectrum. Signs of coupling constants do not influence the spectral pattern hence are not
accessible by standard 1D NMR. Double resonance techniques and 2D NMR may be used to
determine the relative signs for JAX, JAM and JMX. We will learn more about those advanced
techniques in subsequent chapters.
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The 12 resonance lines from the AMX spectrum are described by explicit algebraic equations for
the “effective Larmor frequencies”:
A Part M Part X Part
1 1 1 1 1 1
[1] ν a1 =ν A + JAM + JAX [5] νm1 =νM + JAM + JMX [9] ν x1 =ν X + JAX + JMX
2 2 2 2 2 2
1 1 1 1 1 1
[2] ν a2 =ν A + JAM − JAX [6] νm2 =νM + JAM − JMX [10] ν x2 =ν X + JAX − JMX
2 2 2 2 2 2
1 1 1 1 1 1
[3] ν a3 =ν A − JAM + JAX [7] νm3 =νM − JAM + JMX [11] ν x3 =ν X − JAX + JMX
2 2 2 2 2 2
1 1 1 1 1 1
[4] ν a4 =ν A − JAM − JAX [8] νm4 =νM − JAM − JMX [12] ν x4 =ν X − JAX − JMX
2 2 2 2 2 2
If all signs are positive the series n1 to n4 is decreasing monotonously for each nucleus A, M and X
resp. If all signs are negative the series n1 to n4 is increasing monotonously for each nucleus A, M
and X.
Show by calculation, that the apparent pattern of a first order AMX spectrum is invariant to signs of
coupling constants. But signs will affect the labeling of those 12 lines.
7.1.1 Practical Examples
Heteronuclear AMX Homonuclear AMX
Cl H H
1 13 19
H C F C C
Cl H C C COOH
O
Cl
Cl
H H
1 31
H C P(O)Cl2
19
F
I Br
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Heteronuclear AMX Heteronuclear AMX
H
CH2=CBr-P(O)(OR)2
Cl F
CHBr=CH-P(O)(OR)2 cis
CHBr=CH-P(O)(OR)2 trans
Cl Cl
Heteronuclear AMX Heteronuclear AMX
CH2=CFCl CF2=CHCl
CHF=CHCl cis CHF=CClF cis
CHF=CHCl trans CHF=CClF trans
7.1.2 600 MHz 1H NMR Spectrum of 2-Furoic Acid – a Homonuclear AMX

System
1
The 600 MHz H NMR spectrum of 2-furoic acid reveals a classical AMX system having a total of
12 lines listed and shown in graphics below. Spins are assigned according to:
HX HM
C C
HA C C COOH
O
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NMR data are given by:
Parameter Data
δ1 7.79 [ppm]
δ2 7.26 [ppm]
δ3 6.63 [ppm]
ν1 4674.00 [Hz]
ν2 4356.00 [Hz]
ν3 3978.00 [Hz]
J12 0.90 [Hz]
J13 1.70 [Hz]
J23 3.50 [Hz]
HWB 0.30 [Hz]
Characteristic r-values are calculated: r12 = 367, r13 = 409, and r23 = 105, indicating a suitable AMX
1
character for the 600 MHz H NMR spectrum of furoic acid.
3 4
Remember: All signs of coupling constants JHH (ortho) and JHH (meta) are positive for this furane
compound.
1
Simulation of this 600 MHz H NMR spectrum of 2-furoic acid yielded the graphics shown below:
7.8 7.6 7.4 7.2 7.0 6.8 6.6

(ppm)
Figure 45 : Total spectrum
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4678 4676 4674 4672 4670

(Hz)
Figure 46 : A part of AMX
4360 4358 4356 4354 4352

(Hz)
Figure 47 : M part of AMX
3982 3980 3978 3976 3974

(Hz)
Figure 48 : X part of AMX
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Frequencies and corresponding chemical shifts for transitions of this AMX spectrum are listed
below:
Line νH δH
[Hz] [ppm]
1 4675.295 7.792
2 4674.398 7.790
3 4673.603 7.789
4 4672.707 7.787
5 4358.201 7.263
6 4357.311 7.262
7 4354.702 7.257
8 4353.812 7.256
9 3980.589 6.634
10 3978.891 6.631
11 3977.091 6.628
12 3975.392 6.625
Analyze the AMX spectrum and confirm parameters given above. Within this context it is
convenient to use Peak Picking prior to manual analysis of repeated spacings to extract coupling
constants. Even more effective is the Multiplet Analysis tool provided in the Bruker TopSpin
Software leading directly to resonance frequencies νH, chemical shifts δH, and coupling constants
JHH. After successful analysis the following data for transition frequencies and transition intensities
for an AMX system are calculated:
AMX ABC
Line Frequency Intensity Frequency Intensity
[Hz] [Hz]
1 4675.3000 1.0000 4675.3017 0.9947
2 4674.4000 1.0000 4674.4016 1.0004
3 4673.6000 1.0000 4673.6017 0.9996
4 4672.7000 1.0000 4672.7017 1.0053
5 4358.2000 1.0000 4358.2075 0.9935
6 4357.3000 1.0000 4357.3075 0.9880
7 4354.7000 1.0000 4354.7075 1.0121
8 4353.8000 1.0000 4353.8074 1.0064
9 3980.6000 1.0000 3980.5908 1.0117
10 3978.9000 1.0000 3978.8909 1.0068
11 3977.1000 1.0000 3977.0908 0.9931
12 3975.4000 1.0000 3975.3909 0.9883
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Comparing calculated data for an ABC case shows only minute deviations from the idealized AMX
situation. Corresponding transition frequencies differ by less than 0.01 Hz and intensities by ca.
1
0.01 relative units or less. Hence for practical purposes it was justified to handle the 600 MHz H
NMR spectrum of 2-furoic acid as an AMX case.
7.1.3 Some Complications with Homonuclear AMX Spectra
1
The patterns of 200 MHz H NMR spectra from CH2Br-CHBrCOOH are strongly solvent dependent.
Solutions in D2O, CD3OD, CD3COCD3, CDCl3, and C6D6 will give rise to ABC spectra with
1
considerable ABX to AMX approximation. But luckily, the 500 MHz H NMR of 1,2-dibromo-
propionic acid in CDCl3 will serve as a suitable model to study approximately an AMX analysis
followed by an ABC iteration. After some work we will find the descriptive r-values: r12 = 25.7,
r13 = 92.2, and r23 = 10.7, indicating an AMX with some ABC character.
4.4 4.2 4.0 3.8

(ppm)
1
Figure 49 : 500 MHz H NMR spectrum of 1,2-dibromopropionic acid in CDCl3
The following notation will be used throughout this manuscript:
Left H1 A Part
Middle H2 M part with Some B-character
Right H3 X part with Some C-character
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Transition frequencies may be evaluated from the Peak Picking list:
Peak Picking
Transition
Peak Chemical Shift Intensity
Frequency
[Hz] [ppm] [Rel.]
1 2249.17 4.4972 78.9
2 2244.84 4.4885 87.6
3 2237.88 4.4746 92.9
4 2233.53 4.4659 86.8
5 1961.18 3.9213 79.2
6 1951.07 3.9011 100.0
7 1949.89 3.8988 75.1
8 1939.77 3.8785 89.0
9 1849.36 3.6978 90.4
10 1845.01 3.6891 92.8
11 1839.25 3.6775 79.2
12 1834.89 3.6688 74.3
Try your hand on a (time consuming) manual analysis using an AMX approximation for the 500
1
MHz H NMR spectrum of 1,2-dibromopropionic acid in CDCl3 shown above.
Compare these results with data accessible via spectral deconvolution.

1
Transition frequencies, transition intensities and line specific half widths from this 500 MHz H NMR
spectrum of 1,2-dibromopropionic acid in CDCl3 may be obtained by applying the Bruker tool
DECONVOLUTION yielding an averaged HWB of 0.55 Hz.
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Three-Spin Systems
Deconvolution
Transition
Line Chemical Shift Width Integral
Frequency
[Hz] [ppm] [Hz] [rel.]
1 2249.19 4.4972 0.56 23.58
2 2244.84 4.4885 0.52 24.31
3 2237.89 4.4746 0.51 25.73
4 2233.55 4.4659 0.57 26.37
5 1961.19 3.9214 0.56 23.71
6 1951.08 3.9011 0.61 30.81
7 1949.87 3.8987 0.50 18.94
8 1939.79 3.8786 0.56 26.55
9 1849.37 3.6978 0.57 27.50
10 1845.02 3.6891 0.55 27.11
11 1839.26 3.6776 0.55 23.00
12 1834.92 3.6689 0.57 22.39
It is more convenient to apply the Bruker tool Multiplet Analysis to obtain NMR chemical shifts and
absolute values of coupling constants.
Results from Multiplet Analysis
Chemical Coupling
Data [ppm] Data [Hz]
Shift Constant
δ1 4.4816 |J12| 11.2935
|J13| 4.3343
δ2 3.8999 |J12| 11.2833
|J23| 10.1031
δ3 3.6833 |J23| 10.1133
|J13| 4.3546
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Resonance Frequencies and Averaged Coupling Constants from Multiplet Analysis
Resonance Coupling
[ppm] [Hz]
Frequency Constant
ν1 2230.80 |J12| 11.2884
ν2 1949.95 |J13| 4.3445
ν3 1841.65 |J23| 10.1082
With all couplings constants set positive an AMX iteration was performed for the 500 MHz H NMR
spectrum of 1,2-dibromopropionic acid in CDCl3.
4.6 4.4 4.2 4.0 3.8 3.6

(ppm)
Figure 50 : AMX iteration – all coupling constants set positive. Upper: experimental. Lower: iterated.
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Numerical Results from AMX Iteration with all Couplings Constants Set Positive
Parameter Best Values Error

δ1 4.48272
δ2 3.9010
δ3 3.6843
ν1 2241.36178 0.00006
ν2 1950.47902 0.00006
ν3 1842.13097 0.00006
J12 11.30114 0.00008
J13 4.34338 0.00008
J23 10.10300 0.00008
HWB1 0.53619 0.00013
HWB2 0.55550 0.00010
HWB3 0.55203 0.00013
Baseline Offset 0.01866 0.00127
Baseline Ascent 0.00008 0.00000
Further Parameters to Characterize the Accuracy of the AMX-fit
Digital resolution [Hz/Point] 0.02035

rms 1.07613077
R-Factor [%] 1.446525
The experimental spectrum was measured with a digital resolution of 0.02035 Hz/Point. The AMX-
model fits agreeably well for frequencies, but NOT well enough for intensities.
Hence an ABC Iteration is requested which will fit the transition and simultaneously the intensities.
But prior to this step signs of coupling constants need some considerations.
While the pattern of an AMX spectrum is not affected by signs of coupling constants JAM, JAX, JMX,
the ABC system needs correct assignments for JAB, JAC, and JBC.
The signs of coupling constants may be determined experimentally by classical double resonance
methods in 1D NMR techniques or by more modern 2D NMR techniques. Particularly useful is the
phase sensitive HH-COSY-45 experiment as will be shown below. Corresponding spectra showed,
that sign(J12) is equal to sign(J13) while sign(J12) is unequal to sign(J23).
For details of those techniques see the following chapter.
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A more practical solution will be found by comparison with similar model systems and empirical
rules for chemical shifts and coupling constants. Proton H1 is affiliated with the tertiary hydrogen
atom in CHBrCOOH, while protons H2 and H3 correspond to the pair of geminal hydrogen atoms in
CH2Br.
H2 H1
H3 C C COOH
Br Br
3
Hence J12 and J13 are vicinal coupling constants of type JHH and affiliated with positive signs. J23
2
corresponds to a geminal coupling constant JHH which is known to bear a negative sign in
aliphatic CH2-CH structures. These conclusions are correct as will be deduced from the phase
sensitive 500 MHz HH-COSY-45 spectrum of 1,2-dibromopropionic acid in CDCl3 shown later in
this chapter.
Corresponding iteration lead to final parameters fitting agreeably the experimental spectrum as
shown below:
4.6 4.4 4.2 4.0 3.8 3.6

(ppm)
Figure 51 : ABC iteration – using correct signs for coupling constants. Upper: experimental. Lower:
iterated.
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4.52 4.50 4.48 4.46 4.44

(ppm)
Figure 52 : ABC iteration – A part. Upper: experimental. Lower: iterated.
3.94 3.92 3.90 3.88

(ppm)
Figure 53 : ABC iteration - B part with dominant M-character. Upper: experimental. Lower: iterated.
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3.72 3.70 3.68 3.66

(ppm)
Figure 54 : ABC iteration - C part with dominant X-character. Upper: experimental. Lower: iterated.
Results from ABC Iteration
Parameter Best Values Error

δ1 4.4825 [ppm]
δ2 3.9007 [ppm]
δ3 3.6848 [ppm]
ν1 2241.23906 0.00005 [Hz]
ν2 1950.34930 0.00005 [Hz]
ν3 1842.37823 0.00005 [Hz]

J12 11.32258 0.00007 [Hz]
J13 4.32578 0.00007 [Hz]
J23 -10.10701 0.00007 [Hz]
HWB1 0.53646 0.00011 [Hz]
HWB2 0.55527 0.00011 [Hz]
HWB3 0.55258 0.00011 [Hz]
Baseline Offset 0.01862 0.00106
Baseline Ascent 0.00008 0.00000
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Further Parameters to Characterize the Accuracy of the ABC-fit
Digital Resolution [Hz/Point] 0.02035

rms 0.74577657
R-Factor [%] 0.690480
Note: ABC iteration yields smaller values for the rms and R-factor than AMX iteration. Hence the
ABC model is more correct than the AMX approximation. But do those small differences matter in
practice?
Comparison of Results from AMX and ABC Iterations
Parameter Best AMX Best ABC

δ1 4.48272 4.4825 [ppm]
δ2 3.9010 3.9007 [ppm]
δ3 3.6843 3.6848 [ppm]
ν1 2241.36178 2241.23906 [Hz]
ν2 1950.47902 1950.34930 [Hz]
ν3 1842.13097 1842.37823 [Hz]

J12 11.30114 11.32258 [Hz]
J13 4.34338 4.32578 [Hz]
J23 10.10300 -10.10701 [Hz]
HWB1 0.53619 0.53646 [Hz]
HWB2 0.55550 0.55527 [Hz]
HWB3 0.55203 0.55258 [Hz]
The final step leads to the assignment of spins H2 and H3 to stereo specific positions of hydrogen
atoms in the methylene group of CH2Br.
This goal can be achieved by looking deeper into the vicinal coupling constants J12 and J13.
In fact up to here we did not determine stationary but dynamically averaged coupling constants
symbolized by <J12> and <J13>.
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Six canonical rotameric forms for two different assignments may be set up as shown below:
Assignment 1
Br H2 H3
Br H1 Br H1 Br H1
H2 H3 H3 Br Br H2
COOH COOH COOH
Rotamer 1 Rotamer 2 Rotamer 3
Figure 55 : Canonical rotamers of 1,2-dibromopropionic acid
Inspecting assignment 1 we can approximate expressions for rotationally averaged coupling

constants:
[13] <J12> = x1 J12(1) + x2 J12(2) + x3 J12(3)

[14] <J13> = x1 J13(1) + x2 J13(2) + x3 J13(3)
And further simplify this standard model of canonical rotamers using two transoid (Jt, Jt´) and four
gauchoid (Jg, Jg´, Jg´´, Jg´´´) couplings:
[15] <J12> = x1 Jt + x2 Jg´ + x3 Jg´´

[16] <J13> = x1 Jg + x2 Jt´ + x3 Jg´´´
Molecular modeling studies deduced, that the statistical probabilities xi of (distorted) rotamers are
expected in the order x1 > x3 >> x2.
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Dihedral
Angles
Hi-C-C-Hj
ij Rotamer 1 Rotamer 2 Rotamer 3

12 174,1° -48,9° +81,0°
13 +48,7° -173,0° -43,4°
Figure 56 : Simulated dihedral angles and rotamers of 1,2-dibromopropionic acid. (Details of molecular
modeling studies are beyond the scope of this paper).
1 2 3 4
Vicinal coupling constants in aliphatic fragments CHR R -CHR R are governed by the dihedral
1 2 3 4
angle of H-C-C-H and further effects originating from substituents R , R , R and R .
Read about Karplus function and the multitude of modified Karplus functions.
Basic results are: Jt > Jg). Hence the rotationally averaged coupling constants will obey:
<J12 > > <J13>. And that is what we see with assignments: H1 = HA. H2 = HM. H3 = HX.
Br HM HX
Br HA Br HA Br HA
HM HX HX Br Br HM
COOH COOH COOH
Figure 57 : Canonical rotamers and spin assignment for 1,2-dibromopropionic acid
Thus we can exclude the alternative assignment 2 with inverted protons (H2, H3 or HM, HX resp.).
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7.1.4 Determination of Signs of Coupling Constants J12, J13, and J23
The 500 MHz HH COSY-45 of 1,2-dibromopropionic acid in CDCl3 as an example for the
determination of signs of coupling constants J12, J13, and J23.
Sign(J13) Not equal Sign(J23)

Sign(J12) Not equal Sign(J23)
Sign(J12) Equal Sign(J13)
Figure 58 : 500 MHz HH COSY-45 of 1,2-dibromopropionic acid in CDCl3. Inspect tilts and find relative
signs: J13 vs. J23. J12 vs. J23. vs. J12 vs. J13.
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Remarks and Suggested Reading
Determination of Signs of Coupling Constants

Useful materials on experiments and literature references are described by S. Braun, H.-O.
Kalinowski and S. Berger in “100 and more basic NMR experiments”. VCH, Weinheim, 1996.
CH2Br-CHBr-COOH is discussed in the following sections: a) Homonuclear SPT, pp. 81-83.
b) Phase sensitive COSY, pp. 289- 291. c) Phase sensitive COSY-45, pp. 292- 293.
Corresponding Literature
Homonuclear SPT: a) K. G. R. Pachler, P. L. Wessels, J. Magn. Reson. 1973, 12, 337-339.
b) M. L. Martin, J. J. Delpuech, G. J. Martin, Practical NMR Spectroscopy, Heyden, London, 1980,
222-226
Phase Sensitive COSY: a) D. Marion, K. Wüthrich, Biochem. Biophys. Res. Commun. 1983, 113,
967-974. b) D. J. States, R. A. Haberkorn, D. J. Ruben, J. Magn. Reson. 1982, 48, 286-292.
c) A. E. Derome, Modern NMR Techniques for Chemistry Research, Pergamon, Oxford, 1991, 201-
221. d) M. Eberstadt, G. Gemmecker, D. F. Mierke, H. Kessler, Angew, Chem. Int. Edi. Engl. 1995,
34, 1671-1695
Phase Sensitive COSY-45: a) W. P. Aue, E. Bartholdi, R. R. Ernst, J. Chem. Phys. 1975, 64,
2229-2246. b) A. Bax, R. Freeman, J. Magn. Reson. 1981, 44, 542-561. c) W. E. Hull, in: W. R.
Croasmun, R. M. K. Carlson (eds.), Two Dimensional NMR Spectroscopy, VCH, Weinheim, 1994,
301-303.
Special References for CH2Br-CHBr-COOH

The 300 MHz COSY45 spectrum of 1,2-dibromopropionic acid in C6D6 is described by S. Braun,
H.-O. Kalinowski and S. Berger. “100 and more basic NMR experiments”. VCH, Weinheim, 1996,
p. 289-293.
The 400 MHz COSY45 spectrum of 1,2-dibromopropionic acid is described by W. E. Hull in

“Experimental Aspects of Two-Dimensional NMR”, chapter 2 of “Two-Dimensional NMR
nd
Spectroscopy”. Edited by W. E. Croasmun and R. M. K. Carlson. VCH Weinheim 1994. 2 edition,
pp. 301-303.
Contour plots of the 200 MHz Jeener spectra of 1,2-dibromopropionic acid are discussed by A. Bax
in “Two-Dimensional Nuclear Magnetic Resonance in Liquids”, Delft University Press. D. Reidel
Publishing Company, Dordrecht, 1982, pp. 78-82. A preceding publication is quoted: A. Bax and R.
Freeman; J. Magn. Reson. 44, 542 (1981).
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7.1.5 Double Resonance Experiments and Simulations
J12 and J13 have identical signs. Evidence from Double Resonance spectra.
Irradiation of lines 1 to 4 in A part yields four DR spectra shown below:
1
Figure 59 : 500 MHz H single resonance spectrum of 1,2-dibromopropionic acid in CDCl3.
Compare the unperturbed spectrum with the subsequent double resonance spectra. Lines 1 to 12
are enumerated in order of appearance from left to right.
Double Resonance – Irradiating in A Part – Looking at B Part
1964 1960 1956 1952 1948 1944 1940 1936

(Hz)
Figure 60 : Single resonance spectrum – B part
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1964 1960 1956 1952 1948 1944 1940 1936
1964 1960 1956 1952 1948 1944 1940 1936
1964 1960 1956 1952 1948 1944 1940 1936
1964 1960 1956 1952 1948 1944 1940 1936

(Hz)
Figure 61 : DR spectrum. Expansion of B part. Irradiation at line 1 (upper) to line 4 (lower) of A part.
Double Resonance – Irradiating in A Part – Looking at C Part
1856 1852 1848 1844 1840 1836 1832 1828

(Hz)
Figure 62 : Single resonance spectrum – C part
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1856 1852 1848 1844 1840 1836 1832 1828
1856 1852 1848 1844 1840 1836 1832 1828
1856 1852 1848 1844 1840 1836 1832 1828
1856 1852 1848 1844 1840 1836 1832 1828

(Hz)
Figure 63 : DR spectrum. Expansion of C part. Irradiation at line 1 (upper) to line 4 (lower) of A part.
J13 and J23 Have Opposite Signs. Evidence from Double Resonance Spectra.
1 1
Irradiation of Lines 9 to 12 in C Part Yields Four { H, H} DR Spectra Shown Below:
1
Figure 64 : 500 MHz H single resonance spectrum of 1,2-dibromopropionic acid in CDCl3. Unperturbed
spectrum for comparison with subsequent double resonance spectra.
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Irradiation in X Part – Looking at A Part
2256 2252 2248 2244 2240 2236 2232 2228

(Hz)
Figure 65 : A part unperturbed for comparison
2256 2252 2248 2244 2240 2236 2232 2228

(Hz)
a)
2256 2252 2248 2244 2240 2236 2232 2228

(Hz)
b)
2256 2252 2248 2244 2240 2236 2232 2228

(Hz)
c)
2256 2252 2248 2244 2240 2236 2232 2228

(Hz)
d)
Figure 66 : A part - Irradiation in X part at line: a) 9, b) 10, c) 11, d) 12.
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Irradiation in X Part – Looking at M Part
1964 1960 1956 1952 1948 1944 1940 1936

(Hz)
Figure 67 : M part unperturbed for comparison
1964 1960 1956 1952 1948 1944 1940 1936

(Hz)
a)
1964 1960 1956 1952 1948 1944 1940 1936

(Hz)
b)
1964 1960 1956 1952 1948 1944 1940 1936

(Hz)
c)
1964 1960 1956 1952 1948 1944 1940 1936

(Hz)
d)
Figure 68 : M part - Irradiation in X part at line: a) 9, b) 10, c) 11, d) 12.
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Splitting Pattern for a Hypothetical AMX Case with Sign(JAM) = +, Sign(JAX) = +, Sign(JMX) = -.
A M X
αM βM αA βA αA βA
αX βX αX βX βX αX βX αX βM βM αM αM
Figure 69 : Splitting pattern of an AMX spectrum
We enumerate the lines in the order of appearance from left to right with numbers 1 to 12 and
study the effect of irradiating at line 12 (outmost right) on spectral parts for A and M nuclei. Line 12
corresponds to that effective Larmor frequency of X with spin states αMβA of M and X nuclei.
Hence we expect double resonance effects on lines 1 and 2 for the A part and lines 7 and 8 for the
M part resp. And that is exactly what we see:
2256 2252 2248 2244 2240 2236 2232 2228

(Hz)
1964 1960 1956 1952 1948 1944 1940 1936

(Hz)
Figure 70 : Irradiation at line 12 in X part. Double resonance effects in: A part (upper) and M part
(lower).
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In addition we realize, that we do not need eight DR experiments as done above, two experiments
suffice, as shown e. g. with one of four possible A{X}/M{X} or M{A}/X{A} experiments.
An A{X} / M{X} experiment will yield the relative signs of JAX and JMX. An M{A} / X{A} experiment
will yield the relative signs of JAX and JAM. So omit redundant DR spectra and save time.
Analogous results like double resonance tickling will be achieved with weaker perturbation fields
leading to selective NOE effects in DR spectra. The latter effects and hence the same results for
the assigning the signs of coupling constants can be achieved with modern homonuclear selective
population transfer (SPT) techniques. .
An excellent textbook on experiments and theory is recommended for reading:

J. W. Akitt, B. E. Mann, NMR and Chemistry – An introduction to modern NMR spectroscopy,
Stanley Thornes, Cheltenham, 2000, pp. 236-244.
Acknowledgements
Thanks are due to M. Ackermann (Bruker) for the 500 MHz NMR spectrum of 1,2-di-
bromopropionic acid in CDCl3 and the corresponding HH-COSY-45. Molecular modeling studies
were performed by Th. Thaler (HHUD Düsseldorf).
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7.1.6 Trifluorovinylchloride – a Homonuclear AMX with Minute ABC

Character
19 1
F spins are more sensitive to substituent effects than H spins. Hence asymmetric fluoro-
analogues to standard organic compounds exhibit simpler NMR spectra of higher first order
character.
19
Three F spins in CF2=CClF give rise to the characteristic AMX pattern of a trifluorovinyl function.
At 56.4 MHz this AMX spectrum shows some second order ABC character, but measured at 470
MHz a neat AMX remains.
δ1 δ2 δ3 J12 J13 J23
δF (A) δF (M) δF (X) JAM JAX JMX

-105 -121 -145 78 58 115
[ppm] [ppm] [ppm] [Hz] [Hz] [Hz]
-104 -108 -112 -116 -120 -124 -128 -132 -136 -140 -144 -148
(ppm)
Figure 71 : Total spectrum at 56.4 MHz. Chemical shifts vs. CFCl3.
This three spin system is of minute ABC character only as indicated by weak roof effects. Hence it
may be analyzed directly as AMX system. Iteration as ABC does not change chemical shifts and
coupling constants significantly. Show this by inspection of your own 470 MHz simulation.
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Expansions
-5800 -5840 -5880 -5920 -5960 -6000 -6040

(Hz)
-6720 -6760 -6800 -6840 -6880 -6920 -6960

(Hz)
-8080 -8120 -8160 -8200 -8240 -8280 -8320

(Hz)
Figure 72 : Total spectrum at 56.4 MHz. Expansions: Upper: A part. Middle: M part. Lower: X part
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7.1.7 The 200 MHz 1H NMR Spectrum of Acrylonitrile in CDCl3.
1
The 200 MHz H NMR spectrum of acrylonitrile in CDCl3 shows an AMX system with weak second
order character - a transition to the ABC system. At 500 MHz it becomes a neat AMX system.
HM HX HB HC
HA CN HA CN
AMX ABC
1260 1230 1200 1170 1140

(Hz)
1
Figure 73 : 200 MHz H NMR spectrum of acrylonitrile in CDCl3. Upper: experimental. Lower: simulated.
Common spectral half width: 0.41 Hz.
1
200 MHz H NMR Data for Acrylonitrile in CDCl3
ABC 200 MHz data 500 MHz data

νA 1248.29 [Hz] 3120.71
νB 1218.92 [Hz] 3047.55
νC 1136.25 [Hz] 2840.62

JAB 0.81 [Hz] 0.81
JAC 17.91 [Hz] 17.91
JBC 11.73 [Hz] 11.73
Simulate a corresponding 500 MHz NMR spectrum.

3 3
Remember: In CH2=CHR derivatives the signs of JHH(cis) and JHH(trans) are positive, while
2
JHH(gem) may be either positive or negative depending on R.
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7.2 The ABX System – Spin System No. 6
1 1
2 3 2 3
ABX AXY
Standard ABX spectra exhibit a total of 14 lines. Two equi-intense sets each of 4 lines form the ab
sub-spectra of the AB part. The X part consists of 6 lines symmetrically arranged in 3 pairs around
νX. For clarity we will study the typical ABX system using a simulated spectrum with the following
parameters:
Parameter Data [Hz]

νA +100
νB +95
νX -100
JAB 5
JAX 10
JBX 8
The AB Part
115 110 105 100 95 90 85

(Hz)
Figure 74 : Simulated AB part of the ABX spectrum
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Transition Frequencies and Intensities for the AB Part of the ABX Spectrum
Frequency Intensity
108.4051 0.3598
103.4051 1.6402
100.5949 1.6402
98.7016 0.2191
95.5949 0.3598
93.7016 1.7809
92.2984 1.7809
87.2984 0.2191
The X Part
-85 -90 -95 -100 -105 -110 -115

(Hz)
Figure 75 : Simulated X part of the ABX spectrum
Transition Frequencies and Intensities for the X Part of the ABX Spectrum
Frequency Intensity
-91.0000 1.0000
-92.8933 0.0101
-99.2964 0.9899
-100.7036 0.9899
-107.1067 0.0101
-109.0000 1.0000
The following section will deduce that spectral analysis, which is based solely upon the AB part of
the ABX system, will lead to two different sets of NMR parameters, called the conjugate
solutions. Both solutions will fit all 8 resonance frequencies and intensities in the AB part and all 6
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frequencies in the X part, but will have different intensities in the X part. Hence a unique solution of
the ABX problem will require inspection of both the AB- and the X parts.
Starting Off with the AB Part
The AB part may be broken down into two ab sub-spectra.

Please bear in mind: Total spectra or parts of total spectra (e. g. AB) will be named with capital
letters, sub-spectra (e. g. ab) with lower case letters.
115 110 105 100 95 90 85

(Hz)
Figure 76 : ab sub-spectrum 1
Line Frequency Intensity Type

ν11 108.4051 0.3598 Outer line
ν21 103.4051 1.6402 Inner line
ν31 100.5949 1.6402 Inner line
ν41 95.5949 0.3598 Outer line
115 110 105 100 95 90 85

(Hz)
Figure 77 : ab sub-spectrum 2
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ν12 98.7016 0.2191 Outer line
ν22 93.7016 1.7809 Inner line
ν32 92.2984 1.7809 Inner line
ν42 87.2984 0.2191 Outer line
We will retain the nomenclature introduced in the chapter on AB spectral analysis. Then the
following relations hold:
Sub-spectrum 1 Sub-spectrum 2
[1] si1 = ν21 - ν31 [9] si2 = ν 22 - ν32
[2] so1 = ν11 - ν 41 [10] so2 = ν12 - ν 42
[3] ν z1 = ( ν11 + ν 21+ ν31+ ν 41 ) / 4 [11] ν z2 = ( ν12 + ν 21+ ν32 + ν 42 ) / 4
[4] ∆1 = si1 ⋅ so1 [12] ∆ 2 = si2 ⋅ so2
Ii1 so1 Ii2 so2

[5]
Io1
= si1 [13]
Io2
= si2
[6] J1 = 1
2 ( so1 - si1 ) = JAB [14] J1 = 1
2 ( so1 - si1 ) = JAB
[7] D1 = ν11 - ν31 = ν 21 - ν 41 [15] D2 = ν12 - ν32 = ν 22 - ν 42
[8] D1 = ∆12 + J2AB [16] D2 = ∆ 22 + J2AB
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Following the rules given for AB spectral analysis and defining ν a 1 > ν b 1 , two different
assignments of effective Larmor-Frequencies ν a 2 und ν b 2 are possible:
Figure 78 : Conjugate solutions for ABX systems
Set 1 Sub-spectrum Set 2
[17] νa1 = ν z1 + 21 ∆1 (ab)1 [21] νa1 = ν z1 + 21 ∆1

[18] νb1 = ν z1 - 21 ∆1 (ab)1 [22] νb1 = ν z1 - 21 ∆1
[19] νa2 = ν z2 + 21 ∆ 2 (ab)2 [23] νa2 = ν z2 - 21 ∆ 2
[20] νb2 = ν z2 - 21 ∆ 2 (ab)2 [24] νb2 = ν z2 + 21 ∆ 2
Hence evaluation of transitions will lead to two different parameter sets called the conjugate
solutions of the ABX System. Both alternative solutions are consistent with frequencies and
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intensities appearing in the AB part of the ABX spectrum. In addition both solutions are consistent
with frequencies BUT NOT with intensities of the X part, as we will derive and see below.
Using the following definitions:
Set 1 Set 2
[25] ν z = 1
2 (νA + νB ) [29] ν *z = 1
2 (ν *
A + νB* )
[26] ∆ = ν A - νB [30] ∆ * = 1
2 (ν *
A - νB* )
[27] N = JAX + JBX [31] N* = J*AX + JBX
*
[28] L = JAX - JBX [32] L* = J*AX - JBX

*
The pair of conjugate solutions (set 1 and set 2) is obtained:
[33] ν A = 1
2 ( ν z1 + ν z2 ) + 41 ( ∆1 + ∆ 2 )
[34] νB = 21 ( ν z1 + ν z2 ) - 41 ( ∆1 + ∆ 2 )
Set 1
[35] JAX = ( ν z1 - ν z2 ) + 21 ( ∆1 - ∆ 2 )
[36] JBX = ( ν z1 - ν z2 ) - 21 ( ∆1 - ∆ 2 )
[37] ν *A = 21 ( ν z1 + ν z2 ) + 41 ( ∆1 - ∆ 2 )
[38] νB* = 21 ( ν z1 + ν z2 ) - 41 ( ∆1 - ∆ 2 )
Set 2
[39] J*AX = ( ν z1 - ν z2 ) + 21 ( ∆1 + ∆ 2 )
[40] *
JBX = ( ν z1 - ν z2 ) - 21 ( ∆1 + ∆ 2 )
Combined parameters are used:
Set 1 Set 2
[41] ν Z = 1
2 ( ν z1 + ν z2 ) [45] ν *Z = 1
2 ( ν z1 + ν z2 )
[42] ∆ = 1
2 ( ∆1 + ∆2 ) [46] ∆ * = 1
2 ( ∆1 - ∆2 )
[43] N = 2 ( ν z1 - ν z2 ) [47] N* = 2 ( ν z1 - ν z2 )
[44] L = ∆1 - ∆ 2 [48] L* = ∆1 + ∆ 2
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Both conjugate solutions lead to identical values for the center of the total AB part ν Z , the linear
combinations N, JAB, D1 and D2.
Obviously the ∆* and L* parameters from set 2 are derived from L and ∆ in set 1 by the following
interchange rules:
L
[49] ∆ * =
2
[50] L* =2 ∆
Continuing with the X Part
-85 -90 -95 -100 -105 -110 -115

(Hz)
Figure 79 : Simulated X part of the ABX spectrum
The X Part of the ABX Spectrum

ν13 -91.0000 1.0000 N-line
ν23 -92.8933 0.0101 Outer line
ν33 -99.2964 0.9899 Inner line
ν43 -100.7036 0.9899 Inner line
ν53 -107.1067 0.0101 Outer line
ν63 -109.0000 1.0000 N-line
The X part appears with 6 lines symmetrically arranged in pairs around ν X .
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Three pairs of lines are separated by characteristic splitting si3, so3 and N:
[51] si3 = ν33 - ν 43 = D1 - D2

[52] so3 = ν23 - ν53 = D1 + D2
[53] N = ν13 - ν63 = JAX + JBX
Those three splittings si3, so3, and N are consistent simultaneously with conjugate solutions in set 1
and set 2.
For transition intensities we find:
Set 1 Set 2
[54] I i3 = Io3 = IN [56] I i3* = Io3
*
= IN*
Ii3 1+A+B I 1+A+B
[55]
Io3
= 1- A -B
[57] I i3 = 1- A -B
o3
where auxiliary parameters A and B stand for:
∆ ⋅∆
[58] A = D1⋅D2
1 2
J2
[59] B = D AB
1⋅D2
One set only of the pair of conjugate solutions will be consistent with experimental intensities of the
X part. Hence comparing the experimental and the simulated intensities of the X part will
lead to the correct solution of the ABX problem.
Up to here we have used a hypothetical example as a training case for ABX analysis. For this
situation both conjugate solutions differ in relative signs for coupling constants JAX and JBX.
Set 1 signs for JAX and JBX are identical.

Set 2 signs for JAX and JBX are non-identical.
But when going from set 1 to set 2 of conjugate solutions a change of signs for JAX and JBX is not
compulsory for all ABX problems.
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This may be deduced from:
N
[60] J*AX = +∆
2
N
*
[61] JBX = -∆
2
It is useful to memorize as well:
L
[62] ν *A = ν z +
4
L
[63] νB* = ν z -
4
Those relations may be formulated conveniently in matrix notation following:

[64] P =ν
( A , ν B , J AX , JBX ) parameters for set 1
 * *
P =ν
( A* , ν B* , J AX , JBX )
*
[66] parameters for set 2
where parameters for set 2 are calculated according to:
 
P = LP
* *
[67]
using the transformation matrix L as given by:
 +2 +2 −1 +1

1 +2 +2 +1 −1
[68] L=  
4  −4 +4 +2 +2 
 +4 −4 +2 +2 

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The conjugate solution set 2 is calculated to yield the following parameters:
Parameter Data [Hz]

ν*A 98.000
ν*B 97.000
ν*X -100.000
J*AB -5.000
J*AX 14.000
J*BX 4.000
leading to transition frequencies and intensities:
AB Part: ab Sub-spectrum 1 AB Part: ab Sub-spectrum 2

Frequency Intensity Frequency Intensity
108.4051 0.3598 98.7016 0.2191
103.4051 1.6402 93.7016 1.7809
100.5949 1.6402 92.2984 1.7809
95.5949 0.3598 87.2984 0.2191
X Part
Frequency Intensity
-91.0000 1.0000
-92.8933 0.4900
-99.2964 0.5100
-100.7036 0.5100
-107.1067 0.4900
-109.0000 1.0000
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Simulation with global half width HWB = 0.5 Hz yields the following graphics:
115 110 105 100 95 90 85 80

(Hz)
Figure 80 : The AB part from set 2 is identical with the AB part from set 1 shown in Fig. Simulated AB
part of the ABX spectrum .
-85 -90 -95 -100 -105 -110 -115

(Hz)
Figure 81 : X part from set 2. Please compare and memorize the X part from set 1.
-85 -90 -95 -100 -105 -110 -115

(Hz)
Figure 82 : X part of ABX set 1:
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Obviously we can identify two characteristic situations:
Io3 ≤ Ii3 or
Io3 ≥ Ii3
7.2.1 Practical Examples for ABX Spectra – Homonuclear ABX and AXY
Systems
1. 1H NMR of CH2-CH Fragments - the AXY Case – a Reverse ABX System
2 3
AXY
Sulfonosuccinic acid in aqueous solutions dominantly exists as a univalent anion:
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1
500 MHz H NMR spectra of sulfonosuccinic acid dissolved in D2O exhibit AXY type
4.10 4.00 3.90 3.80 3.70 3.60 3.50 3.40 3.30 3.20 3.10 3.00 2.90
(ppm)
Figure 83 : Total AXY spectrum
Please inspect the expanded A- and XY-regions below:

2043.22
2038.64
2032.69
2028.11
2080 2070 2060 2050 2040 2030 2020 2010 2000 1990
(Hz)
Figure 84 : The A part of an AXY spectrum
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1513.05
1502.45
1495.50
1484.98
1466.44
1461.86
1448.96
1444.39
1520 1510 1500 1490 1480 1470 1460 1450 1440
(Hz)
Figure 85 : The XY part of an AXY spectrum
Analyze the AXY spectrum using the rules given above for ABX cases. Rapid intra-molecular
rotation involving three canonical rotamers I – III create effectively an AXY (rot) system:
I II III
Figure 86 : Canonical rotamers I - III
Determine the resonance frequencies νH and the chemical shifts δH and correlate those data with
the topological positions of protons in the CH2-CH fragment of sulfonosuccinic acid. Determine the
coupling constants JAX and JAY and reflect upon the rotameric equilibrium. Remember the spectral
pattern. It is typical for mono-substituted dicarboxylic acids of type HOOC-CH2-CHR-COOH.
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Malic Acid
1
H NMR spectra of dicarboxylix acids HOOC-CH2-CHR-COOH are governed by protolytic
-
equilibria. Four characteristic species HOOC-CH2-CHR-COOH, OOC-CH2-CHR-COOH,
- - -
HOOC-CH2-CHR-COO , and OOC-CH2-CHR-COO are involved. Varying the pH value of
corresponding aqueous solutions influences the spectral patterns, especially in the CH2-region.
1
This effect is shown by two examples using malic acid (R = OH). Analyze the H NMR spectra.
Please determine the resonance frequencies νH and the chemical shifts δH and correlate those
data with the topological positions of protons in the CH2-CH fragment of malic acid. Determine the
coupling constants JAX and JAY and reflect upon the rotameric equilibrium.
929.08
924.19
922.68
917.72
600.75
595.80
584.13
581.62
579.23
575.22
565.05
558.59
950 900 850 800 750 700 650 600 550

(Hz)
Figure 87 : Malic acid in D2O. 200 MHz AXY spectrum.
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873.62
869.79
864.83
861.01
560.41
556.58
544.66
540.83
515.55
506.70
499.80
490.95
850 800 750 700 650 600 550 500
(Hz)
Figure 88 : Malic acid in excess of 1m NaOD/D2O. 200 MHz AXY spectrum.
2. 19F NMR of CF2-CF Fragments - ABX and AXY Systems
The ABX Spectrum of 1,1,2-Trichloro-2,3,3-trifluorocyclopropane C3Cl3F3
Cl
F1 F3
C
C C
Cl
F2 Cl
F1 F2 F3 J12 J13 J23

-143.2 -136.3 -149.8 155.0 -4.1 -1.3
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19
56.4 MHz F NMR of 1,1,2-trichloro-2,3,3-trifluorocyclopropane (20 % in CS2. Internal standard:
CFCl3) yields a neat homonuclear ABX spectrum:
-136 -138 -140 -142 -144 -146 -148 -150

(ppm)
19
Figure 89 : 56.4 MHz F NMR of 1,1,2-trichloro-2,3,3-trifluorocyclopropane (20 % in CS2)
Expansions of this total spectrum are shown below. We see the classical 8 lines from the AB part
and 4 lines in the X part. Simulate and reanalyze this ABX spectrum.
-7600 -7640 -7680 -7720 -7760

(Hz)
-8000 -8040 -8080 -8120 -8160

(Hz)
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-8400 -8440 -8480

(Hz)
19
Figure 90 : 56.4 MHz F NMR of 1,1,2-trichloro-2,3,3-trifluorocyclopropane (20 % in CS2). A part
(upper), B part (middle), X part (lower) of the ABX spectrum. Resonance frequency [Hz] vs. int.
CFCl3.
From K. L. Williamson und B. A. Braman: “F19 Coupling constants and Chemical Shifts in
Trifluorocyclopropanes”, J. Amer. Chem. Soc. 89, 6183-6186 (1967).
Please bear in mind: Chemical shifts used in this text were adjusted to IUPAC rules: high field
shift = negative shift. The original paper used an outdated definition: high field shift = positive shift.
1,1,2,2,3-Pentachloro-3,4,4-trifluorocyclobutane C4Cl5F3
Cl Cl
F1 F3
C C
C C
Cl Cl
F2 Cl
F1 F2 F3 Standard J12 J13 J23

50.059 58.480 49.533 C6F6 +188.15 +0.83 -13.19
-104.420 -112.841 -113.367 CFCl3 +188.15 +0.83 -13.19
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19
The 56.4 MHz F NMR Spectrum of C4Cl5F3
-102 -104 -106 -108 -110 -112 -114

(ppm)
19
Figure 91 : The 56.4 MHz F NMR spectrum of C4Cl5F3
19
The 56.4 MHz F NMR spectrum of C4Cl5F3 is a tricky case which might be approximated as AXY
but should be iterated as ABC. The ABC type spin system will be studied in details in subsequent
chapters.
Remark: Data from G. Bauer; PhD Thesis 1977, University of Düsseldorf.
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7.2.2 Practical Examples for ABX Spectra – Heteronuclear ABX Systems
F NMR Spectra of an Aqueous Solution of α-Fluoroacrylic Acid Ammonium Salt

1 19
H and
+ -
[NH4] [CH2=CF-COO]
The following figure shows the 200 MHz H NMR spectrum of the α-fluoroacrylate anion in an
1
+ -
aqueous solution of commercially available [NH4] [CH2=CF-COO] .
1100 1080 1060 1040

(Hz)
1 + -
Figure 92 : 200 MHz H NMR spectrum of an aqueous solution [NH4] [CH2=CF-COO] .
This spectrum is a suitable example for an AB part from the total ABX system. Frequencies and
intensities are listed below.
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Transitions from the AB Part (Protons)
ab Sub-spectrum 1
Frequencies Intensities
1112.043 0.951
1108.922 1.049
1048.898 1.049
1045.777 0.951
ab Sub-spectrum 2
1065.539 0.900
1062.418 1.100
1034.336 1.100
1031.215 0.900
Sub-spectral analysis of the AB part leads to the pair of conjugate solutions shown below:
Parameter Solution 1 Solution 2

δA [ppm] 5.4359 5.2782
δB [ppm] 5.2006 5.3582
νA [Hz] 1087.172 1055.638
νB [Hz] 1040.115 1071.649
JAB [Hz] 3.121 3.121
JAX [Hz] 46.544 16.524
JBX [Hz] 14.522 -77.590
Transitions from the X Part (Fluorine)

Solution 1 Solution 2
Frequencies Intensities Frequencies Intensities
4952.826 0.001 4952.826 0.994
4969.467 1.000 4969.467 1.000
4984.030 0.999 4984.030 0.006
5015.970 0.999 5015.970 0.006
5030.533 1.000 5030.534 1.000
5047.174 0.001 5047.174 0.994
Remark: νF is centered arbitrarily at 5000 Hz.
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Simulated X spectra for solutions 1 and 2 are shown in subsequent graphics:
5080 5040 5000 4960 4920

(Hz)
5080 5040 5000 4960 4920

(Hz)
Figure 93 : Simulated X parts for solution 1 (upper), solution 2 (lower).
Correct is solution 1.
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19 1
Heteronuclear ABX System Observed by Proton Decoupled Fluorine NMR F{ H} at 188.28
MHz of P-difluoromethyl-P-phenyl-phosphinic Acid Ethylester
F O
H C P
F OEt
The difluoromethylene group in neighborhood to a chiral phosphorous center exhibits non-

19 1
equivalence effects in the -CF2- unit. Hence a F{ H} NMR spectrum at 188.28 MHz appears in the
19 31
typical ABX pattern (A,B = F. X = P).
5400 5200 5000 4800 4600

(Hz)
19 1
Figure 94 : 188.28 MHz F{ H} NMR spectrum of P-difluoromethyl-P-phenyl-phosphinic acid ethylester.
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5495.417 0.208
5417.690 0.217
5150.417 1.792
5072.690 1.783
5060.083 1.792
4976.810 1.783
4715.083 0.208
4631.810 0.217
Calculate resonance frequencies and coupling constants from data given in table above to find:
Lines Frequency Lines Frequency

11 5495.417 21 5417.690
12 5150.417 22 5072.690
13 5060.083 23 4976.810
14 4715.083 24 4631.810
Results from Sub-spectrum 1 Results from Sub-spectrum 2

So1 780.334 So2 785.88
Si1 90.334 Si2 95.88
JAB 345.000 JAB 345.00
Z1 5105.25 Z2 5024.75
D1 265.500 D2 274.50
νa1 5238.000 νa2 5162.00
νb1 4972.500 νb2 4887.50
The two conjugate solutions are given by:
νA 5200.000 ν∗ A 5062.750
νB 4930.000 ν ∗B 5067.250
JAX 76.000 J*AX 189.800
JBX 85.000 J*BX -350.500
ZAB 5065.000 Z*AB 5065.000
DAB 270.000 D*AB -5.000
But only solution 1 is realistic when referring to NMR data known from organo-fluorine and
organo-phosphorus compounds.
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Finally we inspect the corresponding proton-decoupled phosphorous spectra simulated for

31 1
81 MHz P{ H} NMR:
400 200 0 -200 -400

(Hz)
400 200 0 -200 -400

(Hz)
31 1
Figure 95 : Simulated P{ H} NMR spectrum with data from solution 1 (upper) and solution 2 (lower).
Solution 1 Realistic results Consistent with experimental spectrum
Solution 2 Unrealistic results Not consistent with experimental spectrum
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1
H and 19F NMR: The Tricky ABX Spectrum of 1,1,2-Trichloro-2-fluororethane
Some Problems with Conjugate Solutions

Elemental analysis revealed a compound to be a trichlorofluoroethane C2H2Cl3F.
Three different isomers of C2H2Cl3F may be depicted:
H H H Cl H Cl
Cl C C F Cl C C F F C C Cl
Cl Cl H Cl H Cl
ABX A2X A2X
1
H NMR clearly showed the pattern of a characteristic ABX spectrum, thus excluding two isomers
with twofold symmetry of A2X spin systems. Hence the observed ABX spectrum is due to 1,1,2-
trichloro-2-fluororethane.
NMR studies of this compound proofed to be of intrinsic value for NMR teaching. We will look into
the conjugate solutions of this problem and finally assign the protons to specific positions.
The assignment 1 shown below is correct:
HA HB HB HA
Cl C C FX Cl C C FX
Cl Cl Cl Cl
Assignment 1 Assignment 2
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The AB Part (Protons)
40 20 0 -20 -40
(Hz)
1
Figure 96 : The H NMR spectrum – the AB part of an ABX spectrum.
40 20 0 -20 -40
(Hz)
40 20 0 -20 -40
(Hz)
Figure 97 : The ab sub-spectrum 1 (upper). The ab sub-spectrum 2 (lower).
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Following the ABX-rules discussed above two conjugated solutions were extracted from the
AB part and simulated:
NMR Parameters
Parameters Solution 1 Solution 2

ν1 -9.25 -8.00 [Hz]
ν2 9.25 8.00 [Hz]
ν3 -1000.00 -1000.00 [Hz]

J12 2.80 2.80 [Hz]
J13 44.90 47.40 [Hz]
J23 12.90 10.40 [Hz]
HWB 0.50 0.50 [Hz]
Transitions Frequencies and Intensities
Lines Solution 1 Solution 2

ν11 17.7268 0.2541 17.7268 0.2541
ν21 14.9268 1.7459 14.9268 1.7459
ν31 13.9732 1.7459 13.9732 1.7459
ν41 11.1732 0.2541 11.1732 0.2541
ν12 4.2567 0.9191 4.2567 0.9191
ν22 1.4567 1.0809 1.4567 1.0809
ν32 -30.3567 1.0809 -30.3567 1.0809
ν32 -33.1567 0.9191 -33.1567 0.9191
ν13 -971.1000 1.0000 -971.1000 1.0000
ν23 -980.8164 0.1379 -980.8164 0.8017
ν33 -984.5701 0.8621 -984.5701 0.1983
ν43 -1015.4299 0.8621 -1015.4299 0.1983
ν53 -1019.1836 0.1379 -1019.1836 0.8017
ν63 -1028.9000 1.0000 -1028.9000 1.0000
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Inspect the X parts of both solutions:
-960 -980 -1000 -1020 -1040

(Hz)
-960 -980 -1000 -1020 -1040

(Hz)
Figure 98 : Simulated X part for solution 1 (upper) and solution 2 (lower).
What can we do, if X spectra are not available at the local spectrometer?
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Two routes may lead to the true solution:
1 19
The Fluorine Decoupled Proton Spectrum H{ F} Helps to Solve the ABX Problem:
40 20 0 -20 -40
(Hz)
1 19
Figure 99 : H{ F}: Upper: solution 1. Lower: solution 2. Solution 1 is correct.
Record another AB spectrum at different field strength B0. Here we have increased B0 by a
factor of 5 which leads to the following parameters:
Parameters Solution 1 Solution 2

δ1 -0.0925 -0.0160 [ppm]
δ2 +0.0925 +0.0160 [ppm]
ν1 -46.25 -8.00 [Hz]
ν2 +46.25 +8.00 [Hz]
ν3 -5000.00 -5000.00 [Hz]
J12 2.80 2.80 [Hz]
J13 44.90 121.4 [Hz]
J23 12.90 63.6 [Hz]
HWB 0.50 0.50 [Hz]
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Memorize: The set of coupling constants is invariant for changes of B0. Hence coupling
constants from solution 1 are consistent with the true solution of the ABX problem.
Further Exercises for Heteronuclear ABX Spectra

Compound Chemical Coupling
Shifts Constants
[ppm] [Hz]
H Cl B
δA = 6.275 JAB = - 2.52
C C δB = 6.085 JAX = 15.07
H PCl2 A X δX = arbitr. JBX = 38.40
H2O3P H A X
δA = 3.900 JAB = 64.50
C C δB = 8.500 JAX = 16.80
Br PO3H2 B δX = 6.820 JBX = 11.90
H F X A
δA = 81.90 JAB = 64.5
C C δB = 82.80 JAX = 0.3
Br F B δX = 5.10 JBX = 19.0
H F X A
δA = 129.20 JAB = 137.5
C C δB = 167.70 JAX = 0.0
F Br B δX = 7.50 JBX = 75.0
H Br X
δA = 102.80 JAB = 8.4
C C δB = 154.40 JAX = 13.5
F F B A δX = 6.40 JBX = 72.9
Simulate and reanalyze corresponding spectra.
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Summing Up - Special Cases for ABX Spin Systems - Deceptively Simple Spectra
Formally we can classify different ABX cases according to the number of transitions observed in
the X- and the AB parts.
Number of Lines Comments on Spin System

X Part AB Part
6 8 as 2 ab sub-spectra Standard ABX case.
8 as 2 different ab sub-spectra Special ABX case.
6
both centered around identical νZ N = 0. JAX = JBX.
8 as 2 congruent ab sub-spectra but Special ABX case.
5
centered around individual νZ D1 = D2. L = 0. JAX = -JBX.
AA´X case.
5 8 as 2 congruent ab sub-spectra
D1 = D2. ∆ = 0. JAX = -JBX.
4 as two doublets Special ABX case.
4
for A and B JAB = 0.
AMX case.
4 as doublet of doublets L
4
for A and B
JAB 〈〈 (D ± ) .
2
Special ABX case.
L
3 2 as one doublet only JAB 〉〉 (D ± )
2
A2X case.
3 2 as one doublet only
νA = νB and JAX = JBX.
7.3 The AXX´ System – Spin System No. 7
1 1
2 3 2 3
AXX´ AA´X
The conscious reader will recognize easily that AXX´ is related to AA´X and will refer to the rules
for ABX analysis given in the previous chapter.
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But for didactical reasons the corresponding definitions for AXX´ analysis are repeated below:
[1] N = JAX +JAX´

[2] L = JAX - JAX´
[3] ∆ = νX - νX´ = 0
[4] νz = (νX + νX´)/2 = νX
and for a start we use a hypothetical AXX´ spectrum with parameters:
Resonance Coupling
Data [Hz] Data [Hz]
Frequency Constant
νA 100 JAX´ 10
νX -100 JAX´ 15
νX´ -100 JXX´ 5
The XX´ part of an AXX´ spectrum consists of eight lines, symmetrically arranged around the
center frequency νX, forming two congruent ab type sub-spectra:
Figure 100 : XX´ part of AXX´ spectrum
The absolute value of the coupling constant JXX´ is found four times as a repeated spacing in the
XX´ part following:
[5] JXX´ = ν1i - ν2i = ν3i - ν4i (i = 1,2)
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The centers of those ab type sub-spectra are situated at:
[6] νzi = (ν1i + ν2i + ν3i + ν4i)/4 (i = 1,2)
Both centers are separated by:
[7] νz1 - νz2 = L
Parameters D1 and D2 known from ABX analysis are identical in the AXX´ case:
[8] D1 = D 2 = (L / 2) 2 + J2XX' .
D1 and hence D2 are found from:
[9] D1 = D2 = ν1i – ν3i = ν2i – ν4i (i = 1,2)
Hence we expect five lines for the XX´ part from an AXX´ system (while the AB part of the general
ABX case shows six lines).
Figure 101 : A part of AXX´
Since
[10] D1 - D2 = 0
a singlet at ν33 is found corresponding to the central frequency νA.
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Symmetrically placed around νA is a pair of lines ν23 and ν43 separated by:
[11] ν23 - aν43 = D1 + D2.
Finally the N-lines ν13 and ν53 are evaluated leading to the parameter N:
[12] ν13 - ν53 = N.
Remember: Only absolute values of N and L are found. Hence direct spectral analysis does not
yield a unique solution in JAX and JAX´. But inspection of spectra immediately discriminates between
two alternative solutions:
N>L equal signs sign(JAX) = sign(JAX´)
unequal signs sign(JAX) ≠ sign(JAX´)AX´

N<L
It is useful to evaluate the intensities in the A part which will lead us to the absolute values of
parameters L and JXX´. Using
[13] ν23 – ν43 = So3

I2 + I4 L 2
[14] = R= ( )
I3 2JXX´
The absolute values of L and JXX´ are found from:
R
[15] L = So3
1+ R
So3 1
[16] JXX´ =
2 1+ R
To finish the AXX´ analysis we need to compare the conjugated solution. Following the rules given
in the ABX chapter the parameters for the conjugated solution (*), an AXY type system, are
calculated according to:
[17] ∆* = L/2
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[18] L* = 0.
L
[19] ν∗X = ν X +
4
L
[20] ν∗Y = ν X -
4
JAX + JAX'
[21] J∗AX =J∗AY =
2
An AXY spectrum is found with L = 0 and hence JAX = JAY. Corresponding plots are shown below:
-90 -100 -110

(Hz)
Figure 102 : XY part of the conjugated AXY solution
115 110 105 100 95 90 85

(Hz)
Figure 103 : A part of the conjugated AXY solution.
While the XX´ parts from the AXX´ and the conjugated AXY are congruent, the A parts differ in
intensities. And hence the true solution of the problem will be found by comparison of experimental
and simulated intensities in the XX´- and XY parts resp..
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Analyze the spectra given above using the list of transition frequencies and intensities:
AXX´ AXX´ Conjugated = AXY

Frequency Intensity Line Frequency Intensity Line
112.5000 1.0000 1 112.5000 1.0000 1
105.5902 0.2000 2
100.0000 1.6000 3 100.0000 2.0000 2
94.4098 0.2000 4
87.5000 1.0000 5 87.5000 1.0000 3
-88.4549 0.1056 6 -88.4549 0.1056 4
-93.4549 1.8944 7 -93.4549 1.8944 5
-94.0451 1.8944 8 -94.0451 1.8944 6
-99.0451 0.1056 9 -99.0451 0.1056 7
-100.9549 0.1056 10 -100.9549 0.1056 8
-105.9549 1.8944 11 -105.9549 1.8944 9
-106.5451 1.8944 12 -106.5451 1.8944 10
-111.5451 0.1056 13 -111.5451 0.1056 11
If your analysis is correct, the following parameters should be found:
Parameter AXX´ AXX´ con = AXY

[Hz] [Hz]
ν1 100.0 100.0
ν2 -100.0 -101.25
ν3 -100.0 -98.75
J12 10.0 12.5
J13 15.0 12.5
J23 5.0 5.0
HWB 0.3 0.3
7.3.1 Practical Example
13
The Reverse AA´X System in Pure C Substituted Cis- and Trans-dichloroethylenes
H1 H2 H1 Cl
13 13
C C C C
Cl Cl Cl H2
Cis Trans
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3 3
Both isomers have stereo specific vicinal coupling HH-constants: JHH(cis) and JHH(trans).
Those parameters are easily identified by looking into the ab type sub-spectra in the AA´- part of
3 3
the AA´X spectrum. JHH(cis) and JHH(trans) are found four times as repeated spacings:
1 13
Figure 104 : H NMR spectrum of C-cis-dichloroethylene. AA´ part of AA´X.
1 13
Figure 105 : H NMR spectrum of C-trans-dichloroethylene. AA´ part of AA´X.
We do not need to - and we cannot - evaluate the X parts of those particular AA´X cases, which are
limiting cases with unfavorable intensity relations denying the analytical approach to JAA´. In such
situations intensity measurements are inaccurate.
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13 13
Figure 106 : C NMR spectrum of C-cis-dichloroethylene. X part of AA´X.
13 13
Figure 107 : C NMR spectrum of C-trans-dichloroethylene. X part of AA´X.
Natural Cis- and Trans-dichloroethylenes
12 13
Natural dichloroethylenes consist of 98% all- C-isotopomer, 2% of mono- C-isotopomer,
13 13
neglecting 0.01% of all- C-isotopomer. Hence the standard C NMR spectra of natural
dichloroethylenes will show patterns practically identical with those shown above for
13 12 1 12
CHCl= CHCl. H NMR spectra will show a strong singlet for the dominant all- C-isotopomer
12 12 13 13 12
CHCl= CHCl and in addition C satellites from CHCl= CHCl.
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To identify the stereo isomers of dichloroethylene it suffices to inspect the outer satellite doublet
3 3
exhibiting directly the coupling constant JHH(cis) or JHH(trans) resp. as shown below:
1 13
Figure 108 : H NMR spectrum of natural cis-dichloroethylene. Y-expanded. C satellites - AA´ part of
AA´X.
1 13
Figure 109 : H NMR spectrum of natural trans-dichloroethylene. Y-expanded. C satellites - AA´ part of
AA´X.
NMR Parameters of Cis- and Trans-dichloroethylenes

H1 H2 H1 Cl
13 13
C C C C
Cl Cl Cl H2
Parameters Cis Trans

δA δ1 ppm 6.24 6.28
δA´ δ2 ppm 6.24 6.28
δX δ3 ppm 118.30 120.20

JAA´ J12 Hz 5.5 12.2
JAX J13 Hz 198.5 199.1
JAX´ J23 Hz 16.0 0.8
N Hz 214.5 199.9
L Hz 182.5 198.3
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Some Approximations for Cis- and Trans-ethylene Fragments
1,2-disubstituted cis- and trans-ethylene derivatives may give rise to AA´X or ABX systems as
shown below:
cis cis trans trans
H1 H2 H1 H2 H1 R2 H1 R2
13 13 13 13
C C C C C C C C
R1 R2 R1 R2 R1 H2 R1 H2
1 2 3 4
R ≠R R ≠R
1 2 1 2 1 2 1 2
R =R R =R
Identical Not Identical
AA´X AA´X ABX ABX
13 1 13
Those isotopomers may be monitored as C satellites in H or directly in proton-coupled C NMR
1 1 2
spectra. If H NMR spectra are complicated by resonances from substituents R and R , evaluation
of the AA´ part of AA´X might be obscured. Then the X´ part may serve for a partial analysis of the
AA´X problem.
If we know characteristic values for LAX from practical experience or approximate L by an educated
guess then the following approximations hold:
[22] =L JAX − J A´X
[23] JAX = 1JCH
[24] JA´X = 2JCH

1 1 2
L is dominated by JAX since | JCH| >> | JCH|. Hence L will be around 200 Hz, see results from cis-
13
and trans-dichloroethylene as described above. Then extract So3 from the C NMR spectrum, the
X part of AA´X.
Using
L
So3 2 ( )2 + J2AA´
[25]=
2
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we obtain a reasonable guess for |JAA´|, sufficiently accurate to allow for a stereo specific
assignment of cis- or trans-isomers:
1
[26] JAA´ = (So3 + L)(So3 − L)
2
Remember:
[27] 3JHH
trans
 3JHH
cis
[28] 3JHH
trans
= f ⋅ 3JHH
cis
The empirical factor “f” depends on substituent effects. For trans-dichloroethylenes: f is 2.2.
7.3.2 Further Examples: Tetrachlorobenzenes
Cl Cl Cl
H Cl H Cl H Cl
H Cl Cl Cl Cl H
Cl H Cl
1
Isomeric 1,2,3,4-C6H2Cl4, 1,2,3,5-C6H2Cl4, and 1,2,4,5-C6H2Cl4 give rise to singlets in H NMR
13
spectra. Analyzing corresponding proton coupled C NMR spectra for fragments
13 13 13 n
H- C-C-H, H- C-C-C-H, H- C-C-C-C-H will lead to corresponding JHH data and hence to the
unequivocal identification of molecular structures.
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7.3.3 Further Examples: 2JPP Coupling Constants in P-C-P Structures.
Geminal bisphosphonic acids and related structures have attracted practical interest in medicinal
chemistry. The tetramethylester of methylene-bis-phosphonic acid - a master compound in this
series - is described below:
CH3O H OCH3
O P C P O
CH3O H OCH3
13
Two mayor different natural C-isotopomers exist:
13
CH3O H OCH3 CH3O H OCH3
13
O P C P O O P C P O
CH3O H OCH3 CH3O H OCH3
1% Isotopomer 1 4% Isotopomer 2
13 1 13 1
C{ H}: X Part of A2X C{ H}: X Part of AA´X to ABX
31 1 31 1
P{ H}: A Part of A2X P{ H}: X Part of AA´X to ABX
13 31
Proton-decoupled C and P NMR spectra characterize isotopomer 1 as a simple A2X system
while isotopomer 2 gives rise to AA´X or ABX type systems (depending on field strength and
2
magnetical resolution) which allow direct access to (the absolute values of) coupling constant JPP.
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7.3.4 Further Examples 3: 3JPP Coupling Constants in P-C-C-P Structures.
2 3
JPP is considerably smaller than JPP as can be seen from NMR studies of:
CH3O H H OCH3
O P C C P O
CH3O H H OCH3
13
CH3O H H OCH3 CH3O H H OCH3
13
O P C C P O O P C C P O
CH3O H H OCH3 CH3O H H OCH3
2% Isotopomer 1 4% Isotopomer 2
13 1 13 1
C{ H}: X Part of ABX C{ H}: X Part of ABX
31 1 31 1
P{ H}: X Part of ABX P{ H}: X Part of ABX
While the tetramethylester of 1,2-ethane-bis-phosphonic acid tends to form ABX systems in proton-
13 1
decoupled C{ H} NMR spectra, the free acid and corresponding anions give rise to characteristic
AA´X cases.
1,2-Ethane-bis-phosphonic acid
HO H H OH HO H H OH
13
O P C C P O O P C C P O
HO H H OH HO H H OH
1- 2- 3- 4-
is a four-basic acid conveniently abbreviated as H4L, forming anions H3L , H2L , HL , and L .
Chemical shifts and coupling constants are sensitive to the protolytic state.
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Those parameters can be monitored by NMR-controlled titration.
τ (Degree of Titration)
Figure 110 : JPP vs. τ (degree of titration; equivalents NaOH per unit acid) determined by C{ H} NMR-
3 13 1
controlled titration and subsequent AA´X analysis. See the minimum for τ = 3 (HL ).
3-
13 1
Proton-decoupled C{ H} spectra yielded the X parts of AA´X systems. A typical pattern is shown
below for τ = 0 (the auto protolytic state of H4L).
C{ H} spectrum of 1,2-ethanebisphosphonic acid (τ = 0). X part of AA´X.

13 1
Figure 111 :
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C{ H} NMR controlled titration of 1,2-ethanebisphosphonic acid, (τ = 0 to 6).

13 1
Figure 112 :
Remarks
3
The vicinal JPP depends on the dihedral angle between P-C-C-P showing a KARPLUS type
behavior.
3 3-
The minimum of JPP for HL points towards a gauchoid P-C-C-P conformation possibly stabilized
by hydrogen bridges simplified in the following graphic:
H
O
O
P
H P
H H
n-
while the other protonation states HL (n = 0, 1, 2, 4) will prefer P-C-C-P trans-conformation.
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7.4 The AX2 System – Spin System No. 8
1 1
2 3 2 3
AX2 A2X
A spectrum of this first-order system consists of a triplet in the A part and a doublet in the X part.
ν 1 ν 2 ν3 ν4 ν5
Figure 113 : AX2 spectrum
The absolute value of JAX is found three times as a repeated spacing. A and X parts are centered
around νA and νX resp. as described by the following equations:
[1] |JAX| = ν1 - ν2 = ν2 - ν3 = ν4 - ν5
[2] νA = ν2 = (ν1 + ν3)/2
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[3] νX = (ν4 + ν5)/2
Transition intensities follow:

[4] I1 = I3 = 1 Triplet
[5] I2 = 2 Triplet
[6] I4 = I5 = 4 Doublet
A multitude of practical examples for the A2X case exist, e. g.:
Homonuclear Systems A2X and AX2 Systems

CH2Cl-CHCl2 AX2
CF2Cl-CFCl2 A2X
Heteronuclear A2X Systems
H H
Cl
Cl C F Cl C P
Cl
H H
F Cl
H H H H
Cl Cl Cl Cl
Cl F
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7.4.1 The Homonuclear A2X 19F Spectrum of

1,1,2-Trichloro-1,2,2-trifluoroethane
1
While 1,1,2-trichloroethane CH2Cl-CHCl2 gives rise to an AX2 spectrum in high field H NMR the
fluoro-analogue 1,1,2-trichloro-1,2,2-trifluoroethane CF2Cl-CFCl2
F Cl
Cl C C F
F Cl
19
exhibits an A2X spectrum in F NMR. Corresponding parameters for CF2Cl-CFCl2 were described
for measurements made at 56.4 MHz:
ext ext
δCFCl (CF2 ) =
− 68.5ppm δCFCl (CF) =
− 72.5ppm 3
JFF = ( −)9.5Hz
3 3
Those parameters characterize an A2X spin system having some A2B character. A weak roof
effect and additional splitting are seen from graphics shown below:
-68.0 -69.0 -70.0 -71.0 -72.0 -73.0

(ppm)
19
Figure 114 : 56.4 MHz F NMR spectrum of CF2Cl-CFCl2. Left: A2 part. Right: B part.
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-3844 -3848 -3852 -3856 -3860 -3864

(Hz)
A2 Part of CF2-Group
-4084 -4088 -4092 -4096 -4100 -4104

(Hz)
Figure 115 : B part of CF-group. Line 3 from right corresponds to νB.
For A2B analysis see chapter 7.7 on AB2 and A2B systems.
Those data go back as far as to J. Lee und L. H. Sutcliffe; Trans. Faraday Soc. 55, 880 (1959). But
the authors used the old convention with high field shift = positive shift while we adjusted the table
shown above to the contemporary IUPAC definition: high field shift = negative shift.
3
In addition the authors used a positive coupling constant JFF while later investigations found a
3
negative sign for JFF. (This does not play a role in the present case.
Remember: The sign inside a composite particle B2 or X2 is not accessible by direct analysis of an
AB2 or an AX2 spectrum). Suggestion: Read critically the older literature on chemical shifts and
coupling constants.
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19
But measurements at 470 MHz F NMR yielded a neat first order spectrum A2X for CF2Cl-CFCl2
shown below in two separate parts:
-32210 -32220 -32230 -32240

(Hz)
F NMR spectrum. A2 part of CF2-group. Centered around νA.

19
Figure 116 : 470 MHz
-34090 -34100 -34110 -34120

(Hz)
F NMR spectrum. X part of CF-group. Centered around νX.

19
Figure 117 : 470 MHz
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7.4.2 The Hetero-Nuclear A2X Spectrum of Chlorofluoromethane CH2ClF
Suitable methods may be used to fluorinate methylene dichloride to form chlorofluoromethane

1 19
CH2ClF and difluoromethane CH2F2. CH2ClF gives rise to A2X type spectra in H and F NMR. The
spectral appearance of A2- and X parts are field independent (in contrast to the homonuclear case
CF2Cl-CFCl2 shown above).
Parameter CH2Cl2 CH2ClF CH2F2

δH 5.34 5.92 5.62
δF - -168.9 -142.8
2
JFH - 48 50
Spin System A2 A2X A2X2
Further Examples from Inorganic Chemistry:

19
F NMR spectra of ClF3 measured at lower temperatures and higher fields yield A2B to A2X
patterns. ClF3 is dynamic by pseudo rotation. At room temperature an A3 singlet appears.
Read: Dynamic NMR spectroscopy. Analogous observations were made for RSF3.
F F
Cl F S F
F R F
7.4.3 94 MHz 19F NMR Spectra from the SF3 Part of C6F5-SF3
19
The 94 MHz F NMR spectra from the SF3 part of C6F5-SF3 (solution in toluene, at –50°C) yield the
following data:
δA +73.1 ppm
δX -49.7 ppm
JAX 70.0 Hz
Data from W. A. Sheppard and D. W. Ovenall; Org. Magn. Res. 4, 693-701 (1972)
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70 60 50 40 30 20 10 0 -10 -20 -30 -40 -50

(ppm)
19
Figure 118 : 94 MHz F NMR spectrum. Simulation neglecting all long range couplings between C6F5
and SF3.
6960 6920 6880 6840 6800 6760

(Hz)
19
Figure 119 : 94 MHz F NMR spectrum. A2 part from simulation neglecting all long range couplings
between C6F5 and SF3.
-4560 -4600 -4640 -4680 -4720 -4760

(Hz)
19
Figure 120 : 94 MHz F NMR spectrum. X part from simulation neglecting all long range couplings
between C6F5 and SF3.
Remarks: Fluorine atoms in C6F5 couple weakly with those of the SF3-group. At +20°C the SF3
group remains rigid (no pseudo rotation) while C6F5 rotates around the S-C axis. At elevated
19
temperatures dynamic F NMR spectra are observed.
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7.4.4 A2X Spectra from 31P NMR Studies of Tripolyphosphate Structures
An aqueous solution of pentasodiumtripolyphosphate Na5P3O10 gives rise to A2X spectra as shown

31
in an 81 MHz P NMR simulation:
-600 -900 -1200 -1500

(Hz)
31
Figure 121 : Total 81 MHz P NMR spectrum for Na5P3O10
The P-O-P-O-P Skeleton
O- O- O-
-
O P O P O P O-
O O O
is described by following NMR parameters: δA2 = -6.0 ppm, δX = -20.2 ppm, and JPP(POP) = 19.3
2
31
Hz. This corresponds to an A2X system at 81 MHz P NMR. Minute A2B character is barely visible
and the A2X analysis suffices for this case.
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-440 -460 -480 -500 -520

(Hz)
31
Figure 122 : 81 MHz P NMR A2 part of A2X
-1600 -1620 -1640 -1660 -1680

(Hz)
31
Figure 123 : 81 MHz P NMR X part of A2X.
Tetramminediaquocobalt(III)nitrate was generated from tetramminecarbonatocobalt(III) and reacted

subsequently with pentasodiumtripolyphosphate in strongly acidic solution.
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Two linkage isomers (and further products) were formed:
P NMR identified isomer 1 by an A2X system having chemical shifts δA2 = +0.8 ppm and
31
δX = -21.7 ppm. The complex mixture of products was analyzed by 1D and 2D 31P NMR.
Read the paper by R. N. Bose, A. M. Al-Ajlauni, E. Valkova, J. Chem. Ed. 78, 83-89 (2001) and
reflect upon presentation, completeness and accuracy of this publication.
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7.5 The ABC System – Spin System No. 9
2 3
ABC
Numerous compounds with aliphatic, olefinic, aromatic and heterocyclic structures
R1
H H H H H R2 H H
R1 C C R2 C C
H R3 H R H R3 H S R
or corresponding organo fluorine compounds give rise to ABC spin systems. Substitution patterns
of such compounds were determined successfully using the techniques of ABC analysis followed
by structure specific interpretation of corresponding NMR parameters.
For didactical purposes we will start with a hypothetical ABC spectrum characterized by
Case 1
Parameters Data [Hz]

ν1 10.0
ν2 5.0
ν3 -5.0
J12 5.0
J13 15.0
J23 10.0
HWB 0.3
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This ABC spectrum shows all of the 15 expected lines.
ABC Spectrum Case 1
Figure 124 : Hypothetical ABC spectrum Case 1.
A y-expanded spectrum enhances the weaker lines, which we will need for ABC analysis
Figure 125 : Hypothetical ABC spectrum Case 1. y-expanded.
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Transition frequencies and intensities from ABC spectrum Case 1 are listed in the following table.
Frequency 3 Groups Combination

Line Intensity
[Hz] of 4 Lines Lines
1 29.8721 0.0184 C1
2 23.5150 0.2227 G1
3 15.8245 0.4137 G1
4 15.2663 0.0981 G2
5 12.8229 0.1117 G1
6 7.5758 0.7398 G2
7 5.1325 2.7312 G1
8 3.6488 3.5491 G2
9 1.2187 2.6792 G3
10 -1.2247 0.5561 C2
11 -4.0416 0.0969 G2
12 -9.4733 0.4291 G3
13 -10.3988 0.1282 G3
14 -18.6475 0.0538 C3
15 -21.0908 0.1719 G3
12 main transitions arranged in 4-line groups G1, G2 and G3 (indicated red, blue, green), 3
combination lines C1, C2 and C3. See text below.
This complex multiplet structure might appear to be quite confusing – but only at first sight.
In fortunate cases of less strongly coupled ABC systems, approximations like ABX or even AMX
might hold and allow for a starting evaluation of NMR data following rules given in previous
chapters. Subsequent refinement of starting parameters using suitable NMR programs (see below)
may lead to final and correct data for resonance frequencies and coupling constants. But the
general strongly coupled ABC spectrum is more difficult to understand.
BANWELL and SHEPPARD developed a series of useful rules to analyze ABC spectra:
The ABC system is governed by three resonance frequencies νA, νB, νC and three coupling
constants JAB, JAC, JBC.
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In general an ABC spectrum is characterized by up to 15 lines. For less strongly coupled ABC
spectra three 4-line groups (G1, G2, G3) are recognized and three single combination lines.
Three different separations (S1, S2, S3) are observed as repeated spacings in this ABC spectrum.
Each of those separations is found four times in the experimental or simulated ABC spectrum, but
none is identical to coupling constants JAB, JAC, JBC.
But the sum of separations is equal to the sum of coupling constants.
[1] S1 + S2 + S3 = JAB + JAC + JBC

Frequencies of those three 4-line groups (G1, G2, G3) are symmetrically arranged around centers
(νz1, νz2, νz3).
The centers (νz1, νz2, νz3) are NOT identical with resonance frequencies (νA, νB, νC).
Differences between center frequencies (νz1, νz2, νz3) are NOT identical with differences between
resonance frequencies (νA, νB, νC).
But the sum of center frequencies is identical with the sum of resonance frequencies.
[2] ν z1 + ν z2 + ν z3 =ν A + νB + νC
Three Different Cases are Recognized
Two combination lines are arranged symmetrically around each group and its center νzip.
The separation of two combination lines affiliated specifically with a 4-line group Gi is twice of the
separation of the centers of the two remaining 4-line groups.
n-1
The total intensities of an n-spin spectrum is defined by Inttotal(n) = n 2 . Hence the total intensity
of the ABC spectrum is normalized to 12.
In order to write conveniently some rules for transition intensities the four lines of a 4-line group will
be indexed by subscripts 1 to 4. Then the following rule holds for the intensities of lines 1 and 4 in
groups G1, G2, G3
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[3] I11 + I12 + I13 = I41 + I42 + I43 = 3
3 3
[4] 1i∑
=
=i 1=i 1
I ∑
=
4i I 3
This implies the sum of intensities for the left lines is equal to the sum of intensities for the right
lines in each 4-line group Gi.
Including the combination lines leads to
[5] I21 + I31 + I22 + I32 + I23 + I33 = 6 - IC1 - IC2 - IC3
3 3
[6] 2i ∑I + ∑I
=i 1=i 1
3i =6 − (IC1 + IC2 + IC3 )
3 4
[7] ∑∑ I
=i 1=j 1
ji = 12 − (IC1 + IC2 + IC3 )
This implies the sum of intensities for all four lines Iji of a 4-line group Gi reduced by the sum of
intensities for the adjacent two combination lines is identical for all three permutations of
Gi (I = 1 to 3).
Working with the ABC Spectrum Case 1 Shown in Graphics and Tables Above
Look at the ABC spectrum Case 1. Transitions are enumerated with 1 to 15 from left to right (from
upper to lower frequency). Follow the rules given above to find the three 4-line groups (G1, G2, G3)
and the three combination lines (C1, C2, C3). The graphic below shows the decomposition of ABC
spectrum Case 1 in three 4-line groups and 3 combination lines.
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G1
G2
G3
Figure 126 : The combination lines C1, C2, and C3 are identified as lines ν1, ν10 and ν14 (in the graphic
indicated by circles).
Centers (νz1, νz2, νz3) are found from
Centers From Data [Hz]

νz1 ν1 - ν10 14.3235
νz2 ν1 - ν14 5.6125z
νz3 ν10 - ν14 -9.9360
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Symmetrically arranged around those centers are the 4-line groups (G1, G2, G3)
Groups Transitions
G1 ν2 ν3 ν5 ν7
G2 ν4 ν6 ν8 ν11
G3 ν9 ν12 ν13 ν15
From those 4-line groups (G1, G2, G3) three characteristic separations (S1, S2, S3) are extracted,
each appearing four times as repeated spacing.
Separation Data [Hz]

S1 7.690
S2 10.692
S3 11.618
The sum of separations is determined to
Sum of Sum of
Data [Hz]
Separations Coupling Constants
S1 + S2 + S3 JAB + JAC + JBC 30.0
while the sum of center frequencies yields
Sum of Sum of
[Hz]
Center Frequencies Resonance Frequencies
νz1 + νz2 + νz3 νA +νB +νC 10.0
So far so good, but this is the end of algebraic ABC analysis. We have determined linear
combinations but NOT individual values for coupling constants JAB, JAC, JBC and resonance
frequencies νA, νB, νC.
Continuing the search for coupling constants JAB, JAC, JBC and resonance frequencies νA, νB, νC
may proceed using different routes.
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Route 1
One way to success is to start a series of trial and error calculations with suitable computer
programs, using center frequencies νzi as starting values for resonance frequencies νi and
separations Si for coupling constants Jik. Systematic variations of starting values will lead (in
fortunate cases) to a satisfying congruence of experimental and simulated spectra. Basically two
types of computer programs are available for simulation and iteration of 1D NMR spectra.
Type 1 programs iterate spectra based upon frequencies. Experimental inputs are Lorentzian
peak maxima or better (after deconvolution) transition frequencies. Typical programs: LAOCOON
and its many derivatives (e. g. UEANMR-ITR, NUMARIT) including an advanced version PERCH.
WARNING: ITERATIONS BASED UPON FREQUENCIES ONLY

MAY LEAD TO SETS OF CONJUGATE SOLUTIONS.
Type 2 programs iterate spectra based upon intensities. Experimental input is the total line shape.
Typical programs: DAVINS and modern expansions including chemical and magnetic equivalence,
spins I ≥ ½, using scalar and dipolar coupling (for oriented phases) and an advanced iterator
system, verified as DAISY from WIN-NMR and the more modern TopSpin program suite.
Basic ideas of programs and critical comments on results from iterations will be given in several
chapters of this manuscript.
Route 2
We can simplify the ABC analysis by additional measurements at higher field strength (higher
frequencies). Increasing the spectral relations leads to ABX and AMX approximations, which are
easier to analyze as described in previous chapters. Hence if you meet a complicated ABC system
then look for suitable high field spectrometers in your NMR lab. We will follow this route and work
with the ABC system shown above.
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Increasing the field strength by a factor of 4 (formally going from a 100 MHz to a 400 MHz
spectrometer) increases the resonance frequencies by this factor of 4 leading to the following
parameters used for simulations:
ABC Spectrum Case 2

Parameters [Hz]
ν1 40.0
ν2 20.0
ν3 -20.0
J12 5.0
J13 15.0
J23 10.0
HWB 0.3
80 60 40 20 0 -20 -40
(Hz)
Figure 127 : ABC spectrum Case 2 used for ABX approximation
80 60 40 20 0 -20 -40
(Hz)
Figure 128 : y-Expansion for ABC spectrum Case 2 used for ABX approximation
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ABC Spectrum Case 2 Used for ABX Approximation
Line Frequency Intensity Groups

1 83.0814 0.0010 C1
2 51.1090 0.6246 G1
3 45.7469 0.9042 G1
4 36.7575 0.8409 G2
5 31.3953 1.6106 G2
6 28.1128 0.8030 G1
7 22.7506 0.6967 G1
8 17.8265 1.7305 G2
9 12.4643 0.7874 G2
10 -0.5771 0.0226 C2
11 -9.2218 1.5723 G3
12 -19.5081 0.8762 G3
13 -23.5733 0.9239 G3
14 -33.8596 0.6019 G3
15 -42.5043 0.0040 C3
Analyzing the ABC case 2 as ABX approximation leads to two sets of parameters
Solution 1 (Case 3) for ABX Approximation - AB Part from ABX

Parameter Data [Hz] Parameter Data [Hz]
JAB 5.36 JAB 5.36
So1 28.3584 So2 24.2932
Si1 17.6341 Si2 13.5688
νZ1 36.9298 νZ2 24.6109
∆1 22.3624 ∆2 18.1557
νa1 48.1110 νa2 33.6888
νb1 25.7486 νb2 15.5331
D1 22.9958 D2 18.9304
D1 + D 2 41.9262 D1 - D2 4.0654
Results
νA 40.8999 νB 20.6409
∆AB 20.2590 νZAB 30.7704
JAX 14.4222 JBX 10.2155
N 24.6377 L 4.2067
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These results are consistent with findings from
Solution 1 (Case 3) for ABX Approximation - X Part from ABX

N 24.6378 νZ3 = νX -21.5407
So3 41.9272 Si3 4.0652
and hence support an ABX approximation. Those data allow a better approach for ABC iterations.
But remember; the sign for JAB is not accessible by ABX analysis.
Check the High Field ABC Case 3 by BANWELL Analysis
Check sum Σ νzi νA + νB + νX 40 Hz

Check sum Σ si JAB + JAX + JBX 30 Hz
Obviously ABX solution 1 (case 3) leads to agreeable data for sums of resonance frequencies
and sums of coupling constants resp..
The second solution 2 corresponds to a conjugate solution of the ABX model in Case 3 conj.
Solution 2 (Case 3 Conj.) for ABX Approximation - AB Part from ABX

JAB 5.36 JAB 5.36
So1 28.3584 So2 24.2932
Si1 17.6341 Si2 13.5688
νZ1 36.9298 νZ2 24.6109
∆1 22.3624 ∆2 18.1557
νa1* 48.1110 νa2* 15.5331
νb1* 25.7486 νb2* 33.6888
D1 22.9958 D2 18.9304
D1 + D 2 41.9262 D1 - D 2 4.0654

νA* 31.8221 ν B* 29.7187
∆AB* 2.1034 νZAB 30.7704
JAX* 32.5779 JBX* -7.9402
N 24.6377 L* 40.5181
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Going back to your first spectrometer at lower field strength implies dividing resonance frequencies
by a factor of 4 to calculate Case 4 and Case 4 conj.
Field 1 Field 4 Field 1

Case 3 Case 4
Case 1 Case 2 Case 3 Case 4
conj. conj.
Parameters Data [Hz] Data [Hz] Data [Hz] Data [Hz] Data [Hz] Data [Hz]
ν1 10.0 40.0 40.8999 31.8221 10.25 7.96
ν2 5.0 20.0 20.6409 29.7187 5.16 7.43
ν3 -5.0 -20.0 -21.5407 -21.5407 -5.39 -5.39
J12 5.0 5.0 5.36 5.36 5.36 5.36
J13 15.0 15.0 14.4222 32.5779 14.4222 32.5779
J23 10.0 10.0 10.2155 -7.9402 10.2155 -7.9402
Case 4 is closer to the starting spectrum than Case 4 conj.. So make the data set from Case 4 to
starting values for ABC iterations. Rapid convergence will yield data identical with those shown for
Case 1.
Comparing Case 1 and Case 4
0.30 0.20 0.10 -0.00 -0.10 -0.20
0.30 0.20 0.10 -0.00 -0.10 -0.20

(ppm)
Figure 129 : Upper: starting ABC Case 1. Lower: analysis Case 4. Quite a good start for iterations.
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Remember: Measure an ABC system at two different spectrometer frequencies (field strengths
Bo(1) and Bo(2)). Iterate those spectra. Compare the two sets of coupling constants and resonance
frequencies. If corresponding pairs of coupling constants are identical and corresponding pairs of
resonance frequencies are related by a factor f = Bo(2)/Bo(1) , hence νi(2) = f*νi(1)), then the ABC
problem is solved!
Experiment Field Results

1 Bo(1) νi(1) , Jik(1)
2 Bo(2) νi(2) , Jik(2)
νi(1) / νi(2) = Bo(1) / Bo(2) i = 1 to 3

Jik(1) = Jik(2) i = 1 to 3; k = i+1 to 3
“Virtual Coupling” in ABC Spectra – a Misleading Concept
Consider an asymmetric propane skeleton with three attached protons
H1 H2 H3
C C C
For cases with vanishing coupling constant J13 or J13 = 0 (identical with 13 r → ∞ we do not
1
primarily expect to see additional splitting in the H1 and H3 parts of a H NMR spectrum. But if each
of the pairs (H1 / H2) and (H2 / H3) is strongly coupled, we observe additional, “surprising”, splitting
(in practice often called virtual couplings) in the H1 and H3 parts. Those splittings are field-
dependent and NOT identical with J13.
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See a simulated case, where r12 and r23 were set to 4 and 6 resp..
Parameter Data [Hz]

ν1 240
ν2 200
ν3 140
J12 -10
J13 0
J23 -15
HWB 0.2
Additional Splittings are not Due to Coupling

Additional
Line Frequency Intensity
Splitting
1 245.7647 0.7205
0.3894
2 245.3753 0.7827
3 235.9159 1.2629
0.3894
4 235.5265 1.2251
5 212.5927 1.0411
6 202.7440 0.4839
7 197.8309 1.4557
8 187.9821 1.0281
9 179.4252 0.0096
10 146.6426 1.2385
0.3894
11 146.2532 1.2358
12 131.8807 0.7686
0.3894
13 131.4913 0.7469
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260 240 220 200 180 160 140 120

(Hz)
Figure 130 : Total spectrum regions: left H1, center H2, right H3
248 246 244 242 240 238 236 234 232

(Hz)
Figure 131 : Expansion: left H1. A part. See additional splitting of 0.3894 Hz.
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148 146 144 142 140 138 136 134 132 130
(Hz)
Figure 132 : Expansion: right H3. C part. See additional splitting of 0.3894 Hz.
Do not use the misleading expression “virtual coupling”.

Those splittings are due to second order effects even when J13 = 0 Hz!
7.5.1 Example 1: Ethane Derivates – tBu-CHX-CH2X (X = Cl, Br)
1 2 3 1
Asymmetric derivatives of tris-substituted ethanes CHR R -CH2R give rise to ABC type H NMR
1 3
spectra. Corresponding ABC patterns depend on substituents (R to R ), solvent, concentration
and temperature. An interesting study was presented for 1,2-dihalogenated 3,3-dimethylbutanes,
where a bulky t-butyl substituent is attached to the ethane skeleton.
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1
Simulated 200 MHz H NMR spectra for tBu-CHX-CH2X (X = Cl, Br) are shown below:
800 780 760 740 720 700 680

(Hz)
1
Figure 133 : 200 MHz H NMR spectrum for tBu-CHCl-CH2Cl (1% in CCl4)
800 780 760 740 720 700 680

(Hz)
1
Figure 134 : 200 MHz H NMR spectrum for tBu-CHBr-CH2Br (1% in CCl4)
Corresponding data are listed in the following tables:
NMR Parameters for tBu-CHX-CH2X

Parameters tBu-CHX-CH2X
X = Cl X = Br
ν1 [Hz] 755.00 796.62
ν2 [Hz] 773.32 777.50
ν3 [Hz] 704.36 705.08
J12 [Hz] 3.07 3.62
J13 [Hz] 9.03 9.13
J23 [Hz] -11.53 -11.39
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Transition Frequencies and Intensities for tBu-CHX-CH2X

tBu-CHCl-CH2Cl tBu-CHBr-CH2Br
1 781.0094 0.7541 803.3506 0.7680
2 778.0567 0.9218 799.7619 1.0317
3 770.0143 0.7291 794.3317 0.7711
4 767.0615 1.5418 790.7431 1.4220
5 760.9503 1.3030 785.1640 1.1514
6 757.9976 0.3950 781.5754 0.5450
7 752.3378 1.2134 773.9165 1.3095
8 749.3851 1.1411 770.3279 1.0013
9 722.3446 0.0701 723.7080 0.0132
10 713.2806 1.3168 714.5404 1.2646
11 704.6682 0.9371 705.5215 1.0330
12 702.2855 0.9679 703.2929 0.9226
13 693.6730 0.6911 694.2740 0.7608
14 684.6090 0.0173 685.1064 0.0059
The experimentally observed coupling constants J12, J13, and J23 are dynamically averaged by
rotation.
The rotameric equilibrium may be described by three canonical rotamers (I to III) shown below.
tBu tBu tBu

H3 X H2 H3 X H2
C C C
H1 X H1 X H1 X
H2 X H3
I II III
Coupling constants from tBu-CHX-CH2X indicate dominance of rotamer II. This conclusion was
confirmed by investigations on the deuterated compound tBu-CHX-CHDX giving rise to an AB type
spectrum.
For details read:

a) L. M. Jackson, D. P. Kelly; J. Chem. Soc. (B) 1970, 110-113.
b) M. Buza. E. I. Snyder; J. Amer. Chem. Soc. 88, 1161 (1966). c) References quoted in a) and b).
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Further good examples for ABC spectra are found in compounds like CH2X-CHY-COOH (X, Y =
halogens) and corresponding esters.
7.5.2 Example 2: 200 MHz 1H NMR Spectrum of Styrene in CDCl3 + TMS.
The low field part of this spectrum (7.3 to 7.0 ppm) shows the resonances from the phenyl group in
C6H5-CH=CH2, which gives rise to an [AB]2C system. We will discuss this spectrum in forthcoming
chapters on 5-Spin systems.
The vinyl group, here the main point of interest, exhibits resonances between 5.8 and 5.2 ppm,
representing an ABC spectrum with close proximity to the AMX case.
Hence start AMX analysis and iterate as ABC using DAISY under TopSpin. TopSpin allows for
calculations involving the superposition of different fragments, here the overlap of an [AB]2C and
an ABC part. Rapid convergence in iteration leads to the following spectra and tables:
1500 1400 1300 1200 1100

(Hz)
1
Figure 135 : 200 MHz H NMR of styrene in CDCl3. Upper: experimental. Lower: iterated.
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Results from ABC + [AB]2C Iteration
HC HA
A´ A
C C
B´ B
HB
C
ABC [AB]2C
Vinyl Group ABC

νA 1343.078
νB 1149.087
νC 1047.371
JAB 17.612
JAC 10.897
JBC 0.953
HWB (global) 0.693
Accuracy of parameters: better than ±0.002 Hz.
Phenyl Group [AB]2C

Parameter Data [Hz]
νA 1480.92025
νB 1463.44494
νc 1449.12011
JAB 7.86314 ortho
JAB´ 0.35582 para
JAA´ 2.06405 meta
JBB´ 1.51551 meta
JAC´ 1.19510 meta
JBC 7.43995 ortho
HWB (A) 0.8384
HWB (B) 0.6799
HWB (C) 0.6155
Accuracy of parameters: better than ±0.02 Hz.
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7.5.3 Example 3: 1H NMR Spectrum of 1,2,4-Trichlorobenzene
Cl
HB Cl
HC HA
Cl
1480 1460 1440

(Hz)
Figure 136 : 200 MHz H NMR spectrum of 1,2,4-trichlorobenzene in CDCl3. Signal at δH = 7.252
1
(indicated by arrow), νH = 1451.483 Hz, due to CHCl3, from solvent CDCl3.
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Iterated parameters from TopSpin calculations are shown below (global HWB = 0.645 Hz).
δA 7.4416 δB 7.3517 δC 7.1708 ppm
νA 1489.282 νB 1471.305 νC 1435.092 Hz

JAB n.r. JAC 2.472 JBC 8.607 Hz
n.r.: not resolved in this sample at 200 MHz.
Using a 270 MHz spectrometer the para-coupling JAB was found to be 0.3 Hz. (Thanks are due to
R. Kosfeld for 270 MHz measurements).
7.5.4 Example 4: 1H NMR Spectrum of 1-Chloro-3-bromo-5-iodo-benzene
Cl
HB HA
I Br
HC
4
This is an example with three weak couplings caused by JHH(meta). An AMX type spectrum results
with very low ABC character. For practical purposes (in preparative chemistry) iteration is not
needed. For completeness iterated parameters are given below.
Parameter Data [Hz]

νA 1540.020
νB 1518.780
νC 1486.590
JAB 1.398
JAC 1.708
JBC 1.841
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1540 1520 1500 1480

(Hz)
1
Figure 137 : 200 MHz H NMR spectrum of 1-chloro-3-bromo-5-iodo-benzene in CD3COCD3. (Thanks
are due to H. Dickopp, Düsseldorf, for synthesizing C6H3ClBrI).
12 Calculated Lines Indicating ABC with High AMX Character

1 1541.6088 0.9056
2 1540.2091 1.0306
3 1539.9041 0.9629
4 1538.5045 1.1008
5 1520.4045 1.0026
6 1519.0048 0.8831
7 1518.5618 1.1289
8 1517.1622 0.9855
9 1488.3237 1.0918
10 1486.6190 1.0225
11 1486.4811 0.9720
12 1484.7764 0.9137
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7.5.5 Example 5: Heterocyclic Derivatives – Thiophenes
H4 H3 H4 H3 H4 H3
H5 S Cl H5 S Br H5 S I
H4 Cl H4 Br H4 I
H5 S H2 H5 S H2 H5 S H2
1
Reliable data and interesting methods to analyze H NMR spectra from thiophenes are reported in
“Double and Triple Quantum Transitions in the NMR Spectra of Some Three-Spin Thiophenes”; by
J. J. Jakobsen and J. Aa. Nielsen; J. Magn. Res. 1, 393-405 (1969).
Remarks
Iterations solely based upon frequencies (using LAOCOON type programs) may end up in sets of
conjugate solutions. This situation was met for 2-chlorothiophene where 8 different parameter sets
were iterated. Inspection of spectral intensities between experimental and simulated spectrum will
lead to the true solution of the ABC problem.
1
60 MHz and 100 MHz H NMR spectra of acrylic acid methylester (50% in acetone) lead to two
conjugate solutions for both spectrometer frequencies. If corresponding pairs of coupling constants
are identical and corresponding pairs of resonance frequencies are related by a factor f (f =
Bo(2)/Bo(1) or f*= (νi(2)/νi(1)), then the ABC problem is solved!
For details read: R. J. Abraham, S. M. Castellano; J. Chem. Soc (B), 1970, 49.
What Can be Done to Overcome the Problem of Conjugate Solutions?

a) Measure at highest accessible spectrometer frequency to transform the ABC into an AMX case;
b) Iterate on intensities of the total line shape with TopSpin.
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7.5.6 pH-Dependence of Some ABC Spectra
An interesting report about “An Analysis of the Proton Magnetic Resonance Spectra of Acrylic Acid
in Solution: A Comparative Discussion of the Methods of the Analysis of ABC Spin Systems” was
given by T. Yamamoto and S. Fujiwara; Bull. Chem. Soc. Jap., 30, 333-343 (1966). Unfortunately
the authors did not reference observed frequencies to a defined internal standard, hence only
differences of resonance frequencies and coupling constants were determined. CH2=CHCOOH
- -
and CH2=CHCOO , abbreviated as HL and L , are characterized by specific sets of NMR
parameters. In aqueous solution a protolytic equilibrium exists with a distribution of species
-
described as molar fractions xHL and xL for the protonated HL and deprotonated L forms resp..
Titrating 1.4 m acrylic acid with 1.4 m NaOH to defined pH values lead to the following data and
spectra. pKa = 4.55. At pH 4.59 an AA´B case occurs while in all other situations , ABC and BAC
spectra were observed. We will discuss the AA´B spin system separately in the following chapter.
System pH xHL xL νA νB νC JAB JAC JBC

ABC 2.05 0.994 0.006 24.842 10.475 0 17.271 10.559 1.272
AA´B 4.59 0.313 0.687 22.901 22.901 0 17.448 10.484 1.456
BAC 13.60 0.000 1.000 22.010 28.600 0 17.520 10.450 1.540
50 40 30 20 10 0 -10 -20 -30 50 40 30 20 10 0 -10 -20 -30 50 40 30 20 10 0 -10 -20 -30

(Hz) (Hz) (Hz)
pH = 2.05 pH = 4.49 pH = 13.60
1
Figure 138 : 60 MHz H NMR spectra of acrylic acid adjusted to pH 2.05, 4.49, and 13.60.
This early publication has intrigued us to start a 200 MHz study using NMR controlled titration
technology. The following chemical shifts were obtained for the ABC systems.
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1
200 MHz H NMR Spectra of Acrylic Acid and Acrylate Anion
H H 3 1 C B
H COOH 2 COOH A COOH
H H 3 1 C A
- - -
H COO 2 COO B COO
Figure 139 : Upper: Acrylic acid. Lower: Acrylate anion. See the cross over of protons H1 and H2.
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1 -
H NMR Parameters for CH2=CHCOOH and CH2=CHCOO .
Acrylic Acid Acrylate Anion

Proton ppm ppm
H1 6.128 B 6.070 A
H2 6.374 A 5.962 B
H3 5.952 C 5.599 C
Referenced vs. internal (CH3)3Si-CD2-CD2-SO3Na.
7.5.7 500 MHz 1H{31P} Decoupled NMR Spectra of Vinyl Phosphonic Acid
1
Vinyl phosphonic acid and anions give rise to interesting complex ABCX H NMR spectra which will
be discussed in the chapters dealing with 4 spins.
1 31
Within this context we will concentrate on the phosphorus decoupled H{ P} NMR spectra
representing ABC type and related cases.
The vinylic protons in vinyl phosphonic acid CH2=CHPO3H2 give rise to a strongly coupled ABC
- 2-
part. Anions CH2=CHPO3H and CH2=CHPO3 form ABC systems showing close proximity to AMX,
hence are less strongly coupled.
H H H H H H
C C C C C C
H PO3H2 H PO3H- H PO32-

- 2-
H2L HL L
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1 31
500 MHz Data from H{ P} NMR Spectra of Vinyl Phosphonic Acid and Anions
-- 2-
H2L HL L
- 2-
CH2=CHPO3H2 CH2=CHPO3H CH2=CHPO3
ν1 [Hz] 3126.83 3075.19 3068.08
ν2 [Hz] 3240.59 2943.91 2847.26
ν3 [Hz] 3123.97 2897.32 2776.97

J12 [Hz] 18.809 18.857 18.892
J13 [Hz] 13.015 12.842 12.776
J23 [Hz] 1.371 2.337 3.01
3100 3000 2900 2800

(Hz)
1 31 2-
Figure 140 : 500 MHz H{ P} NMR spectrum for CH2=CHPO3
3100 3000 2900 2800

(Hz)
1 31 -
Figure 141 : 500 MHz H{ P} NMR spectrum for CH2=CHPO3H
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3100 3000 2900 2800

(Hz)
1 31
Figure 142 : 500 MHz H{ P} NMR spectrum for CH2=CHPO3H2
3160 3150 3140 3130 3120 3110

(Hz)
1 31
Figure 143 : Expanded 500 MHz H{ P} NMR spectrum for CH2=CHPO3H2.
Remember: Define the state of solution accurately prior to NMR measurements.
What can we do if direct analysis of low field ABC does not yield reasonable results and
high field spectrometers are not accessible?
If we cannot convert ABC into ABX or AMX (by high field spectrometers) the method of spectral
moments may lead to resonance frequencies ν A, νB, and νC, but NOT to coupling constants JAB,
JAC, and JBC.
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7.5.8 Spectral Moments of ABC Spectra
Spectral moments of order n are defined by
∑ν n
i
Ii
[1] Mn = i
∑I i
i
The first moment M1 is identical with the central frequency νz
[2] M1 = νz
Figure 144 : Defining the first spectral moment
In a second step the set of frequencies is shifted (formally referenced to νz)
[3] ∆νi = νi - νz
Moments Mn , calculated from ∆νi, are related to moments Mn
[4] M1 = 0
[5] M2 = M2 - M12
[6] M3 = M3 - 3 M2M1 + 2 M13
[7] M4 = M4 - 4 M3M1 + 6 M2M12 - 3 M14
ANDERSON and McCONNEL have shown, that spectral moments of first to third order solely
depend on resonance frequencies νi and not on coupling constants Jik.
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[8] ∆ν1 + ∆ν 2 + ∆ν3 = 0

[9] ∆ν12 + ∆ν 22 + ∆ν32 = 3 M2
[10] ∆ν13 + ∆ν32 + ∆ν33 = 3 M3
This set of equations can be solved graphically. Within this context it is useful to introduce the
reduced third Moment R
M3
[11] R =
(M )
1
2
2
and reduced resonance frequencies Ωi
∆νi
[12] Ωi =
(M )
1
2
2
Hence Ωi are functions of R and can be evaluated using the ANDERSON-McCONNEL nomogram,
shown below.
Figure 145 : The ANDERSON-McCONNEL nomogram: Ωi = f(R)
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R is defined in a range
1 1
[13] − 2≤ R ≤+ 2
2 2
Two limiting cases occur
1
[14] R = − 2 corresponding to A2B or AA´B spin systems
2
1
[15] R = + 2 corresponding to AB2 or AB´B spin systems
2
For all other cases three individual Ωi are related to R, hence ABC spectra result.
Try your hand on the moment method using the following spectrum and list of data:
30 20 10 0 -10 -20
(Hz)
Lines 1 2 34 5 6 7 8 9 10 11 12 13 14 15
Figure 146 : The ABC spectrum used to calculate spectral moments
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Transition Frequencies and Intensities from ABC Spectrum

Line Frequency [Hz] Intensity
1 29.8721 0.0184
2 23.5150 0.2227
3 15.8245 0.4137
4 15.2663 0.0981
5 12.8229 0.1117
6 7.5758 0.7398
7 5.1325 2.7312
8 3.6488 3.5491
9 1.2187 2.6792
10 -1.2247 0.5561
11 -4.0416 0.0969
12 -9.4733 0.4291
13 -10.3988 0.1282
14 -18.6475 0.0538
15 -21.0908 0.1719
This spectrum was discussed above and simulated with parameters
Parameter Data [Hz] Parameter Data [Hz] Parameter Data [Hz]

ν1 10.0 ν2 5.0 ν3 -5.0
J12 5.0 J13 15.0 J23 10.0
and a global HWB of 0.3 Hz.
Numerical Evaluation of Spectral Moments
Results from the method of spectral moments can be improved by solving the cubic equation
numerically
Introducing r
∆ν3
[16] r =
∆ν2
into equation given above leads to
[17] ∆ν1 =- (1+r) ∆ν2
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[18] ∆2ν1 = (1+r)2 ∆2ν2
[19] ∆3ν1 =- (1+r)3 ∆3ν2
and
[20] M2 = ∆2ν2 ((1+r)2 + 1 + r2)
[21] M3 = ∆3ν2 (-(1+r)3 + 1 + r3)
[22] R =
(1+r ) - (1+r )
3 3
(1+r ) + (1+r ) 
3
2 2 2
 
1+ r
[23] Ω1 =
( )
1
 1 + r 2 + (1 + r ) 2  2
 
1
[24] Ω 2 =
( )
1
 1 + r 2 + (1 + r ) 2  2
 
r
[25] Ω3 =
( )
1
 1 + r 2 + (1 + r ) 2  2
 
Since
[26] Ω1 + Ω 2 + Ω3 = 0
[27] Ω1 ⋅ Ω 2 ⋅ Ω3 = R
[28] Ω1 ⋅ Ω 2 + Ω1 ⋅ Ω3 + Ω 2 ⋅ Ω3 = − 3/2
[29] Ωi3 - 3
2 Ωi - R = 0
with
[30] R ≤ 1
2 2
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A suitable program conveniently delivers the solution νA = 10 Hz, νB = 5 Hz, νC = -5 Hz, as shown
in the following plot:
1
Figure 147 : Determination of resonance frequencies using the moment method. Red: the H NMR
spectrum. Blue: tick marks at resonance frequencies.
Write your own program to solve the moment method numerically.
Some Comments on Application of the Moment Method to Experimental Spectra
Accurate measurements of intensities of the experimental ABC are requested. Impurity peaks must
be eliminated. Outer lines have greater influence to the moments than inner lines.
Hence the moment method is restricted to good spectra from desirably pure compounds.
The moment method was applied successfully to analyze the pair of abc sub-spectra from ABCX in
CH2=CHP(O)(OiPr)2. This case will be discussed in details in chapter 8.6.3 of this manuscript.
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7.6 The ABB´ and the AA´B System – Spin System No. 10
1 1
2 3 2 3
ABB´ AA´B
Study the AA´B spectrum shown and listed below:
20 0 -20
(Hz)
20 0 -20
(Hz)
20 0 -20
(Hz)
Figure 148 : AA´B. Upper: total spectrum and HWB = 0.3 Hz; middle: y-expanded; lower: y-expanded
and HWB = 0.05 Hz.
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Parameters Used for Simulation

Parameter [Hz] [Hz]
ν1 10.0 10.0
ν2 10.0 10.0
ν3 -10.0 -10.0
J12 5.0 5.0
J13 10.0 10.0
J23 15.0 15.0
HWB 0.3 0.05
Transition Frequencies and Intensities for the AA´B Spectrum
Line Frequency Intensity Assignment

1 37.2438 0.0082 C1
2 22.8667 0.2309 G1
3 19.0031 0.4741 G2
4 16.3709 0.6701 G1
5 13.0050 0.0154 G2
6 12.5073 0.6116 G2
7 6.5092 2.6731 G2
8 5.3606 3.2713 G1
9 -1.1352 0.0370 G1
10 -1.8698 2.2949 G3
11 -7.8679 0.5698 G3
12 -11.7315 0.4518 C2
13 -15.5123 0.2342 C3
14 -19.3759 0.1675 G3
15 -25.3740 0.2900 G3
Definition: Enumeration of transitions from left to right. Line numbers increasing with decreasing
frequencies.
The AA´B (or ABB´) spectrum is a special case of the general three spin system ABC. It is not
possible to perform a complete direct analysis for AA´B or ABB´ cases of high second order
character. It is recommended to transform AA´B or ABB´ spectra into AA´X or AXX´ cases by
measuring at higher field strengths/frequencies. Then follow the rules provided in chapter 7.3.
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Using some intuition and simplifications the analysis of AA´B or ABB´ spectra may start off from
A2B or AB2 and even from ABX or AXY approximations. Resulting parameters need to be iterated
by suitable computer programs. In addition, the moment method will lead to resonance frequencies
as described in chapter 7.5.8. Those approaches will be illustrated below.
7.6.1 Working through the AA´B Case as ABC Approximation
Following the route shown in chapter 7.5.
1. Three 4-Line Groups
G1 = (ν2, ν4, ν8¸ ν9) G2 = (ν3, ν5, ν6, ν7) G3 = (ν10, ν11, ν14, ν15)
2. Combination Lines
C1 = ν1 = 37.2438 Hz C2 = ν12 = - 11.7315 Hz C3 = ν13 = - 15.5123 Hz
Centers of Pairs of Combination Lines Correspond to Centers of 4-Line Groups:

(C1 + C3)/2 = 10.8658 Hz (C1 + C2)/2 = 12.5762 Hz (C2 + C3)/2 = - 13.6219 Hz
= νz1 = νz2 = νz3
3. Centers of 4-Line Groups
νz1 = 10.8658 Hz νz2 = 12.7562 Hz νz3 = - 13.6219 Hz
The sum of all 3 centers corresponds to the sum of resonance frequencies:

Σνzi = 10.0001 Hz
where Σνzi approximates
a) νA + 2νB for ABB´ cases

or
b) 2νA + νB for AA´B cases.

The differences of pairs of centers are found to be:
νz1 - νz2 = - 1.8904 Hz νz1 - νz3 = 24.4877 Hz νz2 - νz3 = 26.3781 Hz
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4. Separations (Repeated Spacings)
s1 = 6.4958 Hz s2 = 17.5061 Hz s3 = 5.9981 Hz

in groups G1 and G2 in groups G1 and G3 in groups G2 and G3
where Σ si approximates ΣJik and Σ si = 30.0000 Hz
Results from ABC Approximation
NMR Parameters for ABC Approximation

Parameter Parameter Data [Hz]
ν1 νB 10.8658
ν2 νA 12.7562
ν3 νC - 13.6219
J12 JAB 6.4958
J13 JBC 5.9981
J23 JAC 17.5061
Well, since we are not too satisfied with the accuracy of those parameters we start an
7.6.2 A2B Approximation of the AA´B
We need some courage to sum up some pairs of lines in order to describe the A2B approximation
with the following parameters:
AA´B Approximation by A2B

Lines in AA´B Average Results Lines in A2B
[Hz]
ν1 37.2438 ν1
(ν2 + ν3) / 2 (22.8667 + 19.0031)/2 20.9349 ν2
(ν4 + ν6) / 2 (16.3709 + 12.5073)/2 14.4391 ν3
ν7 6.5092 6.5092 ν4
ν8 5.3606 5.3606 ν5
ν10 -1.8692 -1.8692 ν6
(ν11 + ν12) / 2 - (7.8679 + 11.7315) / 2 - 9.5997 ν7
(ν13 + ν14) / 2 - (15.5123 + 19.3759) / 2 - 17.4441 ν8
ν15 - 25.3740 ν9
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and obtain with known rules:
A2B Parameters
Parameter Data [Hz]

νA2 ≅ + 9.9000
νB ≅ - 9.5997
JAB ≅ 12.6435
Better results are obtained for frequencies νA and νB. The value of JAB in this auxiliary A2B case
corresponds approximately to the average (12.5 Hz) of JAB and JA´B in the primeval AA´B case.
Compare both models in the following figure:
30 10 -10
30 10 -10
(Hz)
Figure 149 : upper A2B case. Lower: AA´B case.
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7.6.3 Iteration of AA´B
Two ABC iterations with LAOCOON type programs were performed using the approximative
solutions from ABC or A2B analysis:
Analysis ABC A2B

Parameter Case 1 Case 2
ν1 10.8658 9.9000 [Hz]
ν2 12.7562 9.9000 [Hz]
ν3 -13.6219 -9.5997 [Hz]

J12 6.3958 - [Hz]
J13 5.9981 12.6435 [Hz]
J23 17.5061 12.6435 [Hz]
Both iterations end up in identical parameter sets, which fit the AA´B spectrum nicely. Check it.
7.6.4 The ABX Approximation
Let us use a spectrometer at higher field, e. g. increase the frequency by a factor of 4. Then,
instead of the complex spectrum from Figure 148 : a more simpler pattern is observed, which
resembles the familiar ABX pattern:
50 30 10 -10 -30 -50

(Hz)
Figure 150 : Total AA´B spectrum at higher field approximating the AA´X case.
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55 50 45 40 35 30 25
(Hz)
-25 -30 -35 -40 -45 -50 -55

(Hz)
Figure 151 : Expanded A2 part (upper). Expanded B part, approximating X part (lower).
Apply the rules given in chapter 7.2 to Figure 150 : and Figure 151 : and corresponding data:
NMR Parameters for AA´B Simulation at Higher Field Approximating AA´X
Parameter Data [Hz]

νA 40
νA´ 40
νB -40
JAB 5
JAB 10
JAB 15
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Transition Frequencies and Intensities
Line Frequency Intensity Sub-spectra

1 51.7530 0.1411
2 46.8239 1.5172 Approximated
3 46.6158 1.5424 as ab Type
4 41.6867 0.1826
5 39.9715 0.0605
6 34.8342 2.1959 Approximated
7 33.7427 2.2811 as ab Type
8 28.6055 0.0790
9 -28.5770 1.3417
10 -35.4294 0.2435
11 -40.3585 0.7750 Approximated
as X Part of an
12 -41.6582 0.7313 ABX
13 -46.5873 0.1835
14 -53.4397 0.7251
Assignments Transitions
ab Sub-spectrum 1 ν1 ν2 ν3 ν4
ab Sub-spectrum 2 ν5 ν6 ν7 ν8
x part ν9 ν10 ν11 ν12 ν13 ν14
Results from so si JAB ∆ νC

ab Sub-spectrum [Hz] [Hz] [Hz] [Hz] [Hz]
1 10.0663 0.2082 4.9291 1.4477 46.7199
2 11.3660 1.0915 5.1373 3.5222 34.2885
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Those results lead to:
NMR Parameters from ABX Approximation
Parameters Data [Hz] Data [Hz]
JAB - average 5.0332 5.0332
νA 41.0228 41.7417
νB 39.9856 39.2673
JAX 9.9465 11.3942
JBX 14.9164 13.4687
N 24.8628 24.8628
L -4.9699 -2.0745
And from the X part we obtain:

νX - 41.0084
N 24.8627
The conjugate solution 2 does not fit the given spectrum. Correct is solution 1. Iterative
calculations rapidly converge to final results if data obtained above are used as starting
parameters.
Conclusion
Raising the spectrometer frequency improves the accuracy of approximations. Iterations converge
more rapidly to true solutions of the AA´B case.
We have invested quite some time and tried a variety of approaches to obtain NMR parameters
with LAOCOON type programs. We have learned about the benefit of understanding spectral
structures. But results may be obtained much faster by iterating on the total line shape of spectra.
Try your hand on TopSpin and DAISY to have speedier results.
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7.6.5 Practical Examples for AA´B and ABB´ Spectra
are rare. An interesting problem was introduced by YAMAMOTO and FUJIWARA looking at the
1
3-spin H NMR spectra of acrylic acid.
H H
C C
H COOH
The authors observed, that NMR parameters of aqueous solutions (concentration 10%) strongly
depend on the pH value. Resonance frequencies react more sensitive to changes in pH than
coupling constants.
Parameters pH = 4.37 pH = 5.40

ν3 - ν 1 23.09 ± 0.18 22.30 ± 0.65 [Hz]
ν2 - ν 1 21.85 ± 0.20 27.37 ± 0.83 [Hz]

J12 10.47 ± 0.10 10.54 ± 0.55 [Hz]
J13 1.42 ± 0.16 1.36 ± 0.76 [Hz]
J23 17.36 ± 0.06 17.52 ± 0.41 [Hz]
ABC and (formally) BAC spectra were observed. Interpolation lead to ν2 = ν3 = 22.9 Hz for pH =
4.55. This corresponds to an ABB´ spin system! Unfortunately the authors did not reference the
observed resonance frequencies to an internal or external standard. Only differences of resonance
frequencies were given.
This early paper intrigued us to start a reinvestigation of the acrylic acid / acrylate equilibrium using
modern technologies of NMR controlled titration mentioned in chapters on
• ABC 7.5.6, 7.5.7,
• ABB´ 7.6.5 and
• ABCX 8.6.4.
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1
200 MHz H NMR Spectra of 3-Spin Systems from Acrylic Acid and Acrylate Anion
H H 3 1 C B
H COOH 2 COOH A COOH
H H 3 1 C A
- - -
H COO 2 COO B COO
1 -
Figure 152 : 200 MHz H NMR spectra of CH2=CHCOOH (upper) and CH2=CHCOO (lower). See the
cross over point for resonances of H1 and H2 corresponding to an AA´B case.
Acrylic acid dissolved in D2O yielded an ABC spectrum. The acrylate anion, obtained from a
solution of 1 CH2=CHCOOH + 2 NaOH in D2O, lead to a BAC spectrum.
-
The diagram shown above indicates that one distinct mixture of CH2=CHCOOH and CH2=CHCOO
will yield an AA´B spectrum. See the cross-over of spins H1 and H2 indicated by red and blue lines.
Similar observations were made for vinyl phosphonic acid CH2=CHPO3H2 where the cross-over of
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-
resonance frequencies was observed for CH2=CHPO3H2 and CH2=CHPO3H .
Another example was demonstrated by BISHOP and CAREY for the

1-deutero-1-chloro-2-bromoethane CH2Br-CHDCl:
H H HB HA
Br C C Cl Br C C Cl
H D HB´ D
While Br-CH2-CH2-Cl gives rise to a symmetrical spin system [AB]2 (discussed under 4-spin
problems in this manuscript) the protons in Br-CH2-CHD-Cl form an ABB´ system (neglecting the
2 3 1 2
small proton deuteron couplings ( JDH, JDH) or decoupling the deuterons in a H{ H} double
resonance experiment).
7.7 The AB2 System – Spin System No. 11
1 1
2 3 2 3
AB2 A2B
A typical AB2 spectrum consists of up to 9 lines. But in most cases the weak line no. 9 is not
detected.
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Hence the routine AB2 spectrum is characterized by 8 lines:
Figure 153 : Simulated AB2 spectrum. Weak line no. 9 is indicated by red arrow.
AB2 analysis does neither yield the sign of JAB, nor magnitude and sign of JBB inside the B2-group
(being a composite particle). Inspecting the intensities in an AB2 case will lead to a unique
assignment of A and B2 spins.
Remember: Direct analysis of the simpler AB case does not assign unequivocally spins A and B to
1
the pair of H atoms under consideration in a particular molecular structure, see the chapter 6.2.
Hence two stereo specific solutions are obtained for the AB case.
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The following equations suffice to analyze AB2 spectra solely based upon transition frequencies:
Line Frequency
3
[1] 1 νC + J + C+
4
[2] 2 νB + C+ + C −
[3] 3 νA
3
[4] 4 νC − J + C−
4
[5] 5 νB + C+ − C −
3
[6] 6 νC + J − C+
4
[7] 7 νB − C+ + C −
3
[8] 8 νC − J − C−
4
[9] 9
νB − C+ − C −
where parameters C+, C-, ∆, and νC are given by:
2 9 2
[10] C=
+ 2 ∆ + ∆J + J
1
4
2 9 2
[11] C=
− 2 ∆ + ∆J − J
1
4
[12] ∆ = ν A − νB
1
[13] νC= (ν A + νB )
2
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Use a ruler and your experimental spectrum to find repeated spacings:
1
[14] C+= (ν1 − ν 6 )
2
1
[15] C+= ( ν 2 − ν7 )
2
1
[16] C+= ( ν5 − ν9 )
2
1
[17] C−= ( ν 4 − ν8 )
2
1
[18] C−= ( ν 2 − ν5 )
2
1
[19] C−= ( ν7 − ν9 )
2
If the AB2 spectrum is analyzed correctly, then the proper repeated spacings C+ and C- must be
found.
The center νC of the AB2 spectrum is given by:
1
[20] νC= ( ν 2 + ν9 )
2
1
[21] νC= ( ν5 + ν7 )
2
1
[22] νC= (ν1 + ν 4 + ν 6 + ν8 )
4
The difference of resonance frequencies follows from:
1
[23] ∆= (2ν3 − ν5 − ν7 )
2
Results for AB2 are obtained quickly by evaluating transition frequencies:
[24] ν A =ν3
1
[25] νB= ( ν5 + ν7 )
2
1
=
[26] JAB [(ν1 − ν 4 ) + (ν 6 − ν8 )]
3
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If the AB2 spectrum is analyzed correctly, then the following intensity rules are fulfilled:
[27] I3 =1
[28] I5 -I4 =1
[29] I7 -I1 =1
[30] I4 +I8 =3
[31] I1 +I6 =3
[32] I2 +I5 -I6 =1
[33] I2 +I7 -I8 =1
If you want to learn more about transition intensities from AB2 system use the following
equations:
Line Intensity
[34] 1 ( 2 sin Θ+ − cos Θ+ )2
[35] 2 ( 2 sin(Θ+ − Θ− ) + cos Θ+ cos Θ− )2
[36] 3 1
[37] 4 ( 2 sin Θ− + cos Θ− )2
[38] 5 ( 2 cos(Θ+ − Θ− ) + cos Θ+ sin Θ− )2
[39] 6 ( 2 cos Θ+ + sin Θ+ )2
[40] 7 ( 2 cos(Θ+ − Θ− ) − sin Θ+ cos Θ− )2
[41] 8 ( 2 cos Θ− − sin Θ− )2
[42] 9 ( 2 sin(Θ+ − Θ− ) − sin Θ+ sin Θ− )2
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with trigonometric expressions:

1 1 1 1
∆+ J ∆− J
[43] cos 2Θ+ =2 4 [44] cos 2Θ− =2 4
C+ C−
1 1
∆+ J ∆− J
[45] cos 2Θ+ = 2 [46] cos 2Θ− = 2
9 9 2
∆ + ∆J + J2
2
∆ 2 − ∆J + J
4 4
J J
[47] sin2Θ+ = [48] sin2Θ− =
2 C+ 2 C−
There is more work to do to convert those functions for angles 2Θ+ and 2Θ− into functions for
angles Θ+ , Θ− , and ( Θ+ − Θ− ) resp..
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The algebraic expressions for transition intensities of lines 1 to line 9 in the AB2 case are shown in
the following table:
Line Intensity
∆ 9
3 − − J
[49] 1 + 2 4
2 C+
9 5
5C+ C− + ∆ (C+ + C− − 3 ∆ ) + J (C− − C+ − J)
[50] 2 2 2
4C+ C−
[51] 3 1
∆ 9
3 − 2+ 4J
[52] 4 +
2 C−
9 5
5C+ C− + ∆ (− C+ + C− − 3 ∆ ) + J (C− + C+ + J)
[53] 5 2 2
4C+ C−
∆ 9
3 2+ 4J
[54] 6 +
2 C+
9 5
5C+ C− + ∆ (C+ − C− + 3 ∆ ) + J (− C− − C+ + J)
[55] 7 2 2
4C+ C−
∆ 9
3 2− 4J
[56] 8 +
2 C−
9 5
5C+ C− − ∆ (C+ + C− + 3 ∆ ) + J (− C− + C+ − J)
[57] 9 2 2
4C+ C−
Still laborious to work with! Hence, in practice, we do not evaluate intensities manually - this job is
left to suitable computer programs!
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7.7.1 Practical Examples for AB2 Spectra and the Reverse A2B Case
1
AB2 Pattern in the 200 MHz H NMR Spectrum of 2,6-Dimethoxyphenol (DMOP)
OH
CH3O OCH3
HB HB
HA
1 2 3 4 56 78
1320 1305 1290 1275 1260

(Hz)
1
Figure 154 : 200 MHz H NMR spectrum of 2,6-dimethoxyphenol - an AB2 case
Line Transitions Lorentzian Peaks*

No. Frequency Intensity Frequency Intensity
1 1321.5935 0.5766 1321.59 21.3
2 1314.2697 0.8136 1314.27 30.1
3 1312.0018 1.0000 1312.00 37.0
4 1304.6781 1.6107 1304.68 59.3
5 1284.0172 2.6098 1284.02 100.0
6 1283.3102 2.4234 1283.31 93.5
7 1275.9864 1.5757 1275.99 58.6
8 1274.4256 1.3893 1274.43 51.7
*) Relative intensities of Lorentzian peaks: intensity of strongest peak is defined to 100 by

simulation program.
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Analyze the spectrum of 2,6-dimethoxyphenol using the transition table given above. If your
calculations are correct, you should find the following NMR parameters:
ν1 = 1312.0 Hz ν2 = 1280.0 Hz J12 = 8.6 Hz.
Remember: Only the absolute value for JAB is accessible. The relative sign of JAB follows from
3 ortho
known data for aromatic compounds: the ortho H-H coupling JHH is positive!
Some Comments on Molecular Structures
We have analyzed 2,6-dimethoxyphenol. All the isomers of C6H3(OH)(OCH3)2 are shown in the
following scheme indicating corresponding spin systems.
OH OH
H OCH3 H OCH3
H OCH3 H H
H OCH3
ABC ABC - ABX
OH OH
H OCH3 CH3O OCH3
CH3O H H H
H H
ABC - ABX AB2
OH OH
H H H H
H OCH3 CH3O OCH3
OCH3 H
ABC - ABX AB2 - AX2
Four isomers are associated with ABC to ABX spectra, only two isomers have twofold symmetry in
AB2 and AX2 systems. The 3,5-dimethoxyphenol isomer is characterized by meta H-H couplings
4 meta
JHH in JAB, which are expected to be around 2 Hz, giving rise to weakly coupled systems.
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Hence in example 1 we have deduced the correct molecular structure from a strongly coupled AB2
system.
OH
CH3O OCH3
HB HB
HA
2,6-Symmetrically Disubstituted Pyridines
1
AB2 type H NMR spectra are obtained from 2,6-dichloropyridine when dissolved in CDCl3 and
measured at 200 MHz. The coupling is weaker in 2,6-dimethoxipyridine and hence an AX2
spectrum results with some second order AB2 character.
H H
H H H H
Cl N Cl CH3O N OCH3
Compound νA νB JAB ∆ rAB

[Hz] [Hz] [Hz] [Hz]
2,6-dichloropyridine 1526.57 1456.65 7.70 96.93 9.08
2,6-dimethoxipyridine 1493.28 1257.57 7.88 245.71 31.18
(Thanks are due to H. Weber, Düsseldorf, for pyridine compounds).
Some Comments on Trigonometric Solutions for the AB2 Spectrum
While a simple trigonometric solution for NMR parameters of the AB spectrum was derived, the
situation is more complex for the AB2 situation, see the chapter 6.2.2 above.
Trigonometric solutions do not yield directly the parameters ∆ and J wanted. Only two
combinations of parameters ∆ and J are obtained as shown below.
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Using the parameters found for 2,6-dimethoxyphenol
νA = 1312.0 νB = 1280.0 JAB = 8.6
∆ = 32,0
2
C+ = 17.48142 C+ = 305.6
∆ = 32,0
2
C- = 14.91308 C- = 222.4
and
2 9 2
[57] C=
+ 2 ∆ + ∆J + J
1
4
2 9 2
[58] C=
− 2 ∆ − ∆J + J
1
4
we obtain two auxiliary graphics in:
Figure 155 : Partial solutions to the AB2 problem.
Those graphics represent:
1 2 9 2
[59] C2+ + C2− = ∆ + J
2 8
∆J
[60] C2+ − C2− =
2
and with laborious arithmetic you might land up at additional solutions for ∆ and JAB.
In practice, we do not use the trigonometric method.
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7.7.2 AB2 System in 31P{1H} Spectrum of the Cyclotripolyphosphine

[CH3P]3
CH3 CH3
P H 3C P CH3
P P P P
H 3C CH3
I II
31 1
This cyclotripolyphosphine [CH3P]3 has structure I and not structure II. P{ H} NMR clearly reveals
an AB2 type system for structure I and not an A3 case, which is expected for structure II.
The characteristic NMR data are found:
δA – δB = 3.45 ppm. 1JAB = (-) 168 Hz. δA arbitrarily defined to be 0.0 ppm.
1.0 0.0 -1.0 -2.0 -3.0 -4.0 -5.0

(ppm)
31 1
Figure 156 : 202 MHz P{ H} spectrum of [CH3P]3 – an AB2 case.
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1 23 4 56 78
200 -100 -400 -700 -1000

(Hz)
31 1
Figure 157 : 202 MHz P{ H} spectrum of [CH3P]3
1 2 3 4
56 7 8
150 0 -150 -300 -450

(Hz)
31 1
Figure 158 : 40 MHz P{ H} spectrum of [CH3P]3
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150 0 -150 -300 -450

(Hz)
31 1
Figure 159 : 40 MHz P{ H} spectrum of [CH3P]3. Y-expanded. Transition 9 marked red.
Transition Frequencies and Intensities Calculated for νP 202 MHz and 40 MHz

202 MHz 202 MHz 40 MHz 40 MHz
1 183.0607 0.6629 219.3205 0.1275
2 33.3354 0.8893 145.5018 0.1241
3 0.0000 1.0000 0.0000 1.0000
4 -149.7254 1.4482 -73.8187 2.7629
5 -757.1583 2.4478 -98.5182 3.7483
6 -769.0051 2.3371 -106.9779 2.8725
7 -918.7305 1.6626 -180.7966 1.1130
8 -940.2190 1.5518 -317.8387 0.2371
7.7.3 The A2B Spectrum at 200 MHz from 1,2,3-Trichlorobenzene in CCl4
1
Please look at the 200 MHz H NMR spectrum of 1,2,3-trichlorobenzene representing an A2B
system. Rules for analysis of transition frequencies in the AB2 case hold, when applied in reverse
order, numbering transitions from right to left. Determine νA, νB, and JAB. Check C+ und C-. All
frequencies listed below are referenced to internal TMS.
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Cl
Cl Cl
HA HA
HB
87 65 4 32 1
1470 1455 1440 1425 1410

(Hz)
Figure 160 : The A2B spectrum at 200 MHz from 1,2,3-trichlorobenzene in CCl4
Transition Frequencies and Intensities Calculated for νH 200 MHz
Transitions Lorentzian Peaks

1 1468.8551 1.6222 1468.85 65.5
2 1467.9868 1.7045 1467.99 68.6
3 1460.5397 2.2953 1460.54 97.0
4 1460.0176 2.3776 1460.02 100.0
5 1423.4492 1.3778 1423.45 54.0
6 1416.0021 1.0000 1416.00 39.6
7 1414.6117 0.9177 1414.61 36.4
8 1407.1646 0.7047 1407.16 27.6
Results: νA = 1464 Hz. νB = 1416 Hz. JAB = 8.2 Hz
Analysis of the experimental spectrum from 1,2,3-trichlorobenzene yielded the coupling constant
3
JAB = 8.2 Hz corresponding to the ortho-coupling JHH.
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4
The meta-coupling JHH inside the composite particle is not accessible by standard 1D NMR.
P. Diehl and H. Bösiger determined the meta-coupling by advanced techniques and found
4
JHH = 1.45 Hz.
13
Read: “The use of C satellites in Proton Spectra of Oriented Molecules: The rα-structure of 1,2,3-
trichlorobenzene”, J. Magn. Reson. 35, 367-372 (1979).
4
A reinvestigation by Y. Hiltunen and J. Jokisari lead to JHH = 1.87 Hz.
Read: J. Magn. Reson. 75, 213-221 (1987).
If you want to learn more about
“The determination of aromatic substitution patterns by Nuclear Magnetic Resonance”
read the paper by M. Zanger, Org. Magn. Reson. 4, 1-25, (1972). Chemical shifts and coupling
n
constants JHH are discussed. This paper is quite old – but still useful.
Some Systematic Considerations
In order to understand the spectral habitus of AB2 spectra, a series of NMR spectra were
simulated.
The coupling constant JAB was fixed to 10 Hz in all simulations. The resonance frequency νA was
set to 0 Hz, while νB vas varied from -100 Hz to +100 Hz. Hence the difference of resonance
frequencies ∆ = νA-νB varies between +100 and -100 Hz.
Results from simulations are presented as graphics showing transitions frequencies and intensities
as functions of ∆. 9 different colors were used to indicate the 9 characteristic transitions:
Color Code for Simulations
Line Color
1 green
2 magenta
3 black
4 turquoise
5 brown
6 orange
7 red
8 blue
9 olive
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Remarks: Graphics were plotted with software using the mathematical definition of x-axis: left +,
right -. Hence those simulations appear as mirror images on the usual NMR x-scale.
Changing the Spectral Habitus: from AB2 via AA´2 or A2A´ to A2B
Figure 161 : Simulating AB2 type spectra. 9 Frequencies vs. ∆. Lines are marked:
1 green. 2 magenta. 3 black. 4 turquoise. 5 brown. 6 orange. 7 red. 8 blue. 9 olive.
Figure 162 : Simulating AB2 type spectra. 9 Intensities vs. ∆. Lines are marked:
1 green. 2 magenta. 3 black. 4 turquoise. 5 brown. 6 orange. 7 red. 8 blue. 9 olive.
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These Diagrams Show Clearly:
if then
∆=0 we obtain an AA´2 or A2A´ system characterized by a single line with a total
intensity of 12.
∆ >> |JAB| we obtain an AX2 system characterized by the three A-triplet lines with a total
intensity of 4 and the two X-doublet lines with a total intensity of 8.
−∆ >> |JAB| we obtain an A2X system characterized by the three X-triplet lines with a total
intensity of 4 and the two A-doublet lines with a total intensity of 8.
Remember:
Spectra generated by (∆, JAB) and (-∆, JAB) are mirror images.
Spectra generated by (∆, JAB) and (∆, -JAB) are congruent.
Spectra generated by (n∆, nJAB) and (m∆, -mJAB) are similar.
Signs of coupling constants JAB are not accessible via standard single resonance spectra of
AB2 or A2B cases. Absolute values of JAB are obtained.
Three Examples Using the Following Data from those Simulations
Spectrum ν1 ν2 ∆ = ν1 - ν2 J12 r12 Type System
[Hz] [Hz] [Hz] [Hz]
upper 0 +20 -20 +10 -2 1 A2B
middle 0 0 0 +10 0 2 AA´2 / A2A´
lower 0 -20 +20 +10 +2 3 AB2
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are shown in graphics below:
30 20 10 0 -10 -20 -30
30 20 10 0 -10 -20 -30
30 20 10 0 -10 -20 -30

(Hz)
Figure 163 : Changing the spectral habitus. Upper: type 1 A2B; middle: type 2 A2A´ / AA´2; lower: type 3
AB2.
7.7.4 A2B and AB2 Spectra Approximating A2X and AX2 Cases
For spectral relations even as large as rAB = ±50 we still observe some second order character
indicated by a so called “roof effects”. Please compare graphics shown below simulated with the
following parameters:
Spectrum ν1 ν2 ∆ = ν1 - ν2 J12 r12 Type System
[Hz] [Hz] [Hz] [Hz]
upper 0 -500 +500 +10 +50 1 A2B / A2X
lower 0 +500 -500 +10 -50 3 AB2 / AX2
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400 200 0 -200 -400
400 200 0 -200 -400

(Hz)
Figure 164 : Weak roof effects in weakly coupled systems. Upper: A2B. lower: AB2.
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7.8 The AAÁ´´, AA´2, and A3 Systems – Spin System No. 12, 13, 14
At the end of a systematic treatment of 3 spin cases three trivial spectra remain. Each of the
AAÁ´´, AA´2, and A3 systems gives rise to a singlet, centered around the resonance frequency νA.
Remember: An isolated ensemble of isochronous spins will exhibit a singlet. No information
regarding coupling constants inside the ensemble is available by standard 1D NMR (for samples in
isotropic solutions).
2 3
AAÁ´´
1 1
2 3 2 3
AA´2 A2A´
2 3
A3
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AAÁ´´, AA´2, and A3 Spectra Appear as Simple Singlets
Figure 165 : The singlet line for 3 isochronous spins in AAÁ´´, AA´2, and A3.
Typical examples for A3 are sym-1,3,5-trichlorobenzene C6H3Cl3 and methylchloride CH3Cl.
C l
H H H
H C C
C l C H
in addition: isolated methyl groups, e. g. CH3COOR, RCOOCH3, RCOCH3, ROCH3. Hence

methylacetate CH3COOCH3 will exhibit two separate singlets of equal intensity.
Methyl groups bound to aromatic substituents in Ar-CH3 will exhibit singlets with broadened lines.
n
At good resolution fine splittings with weak long range couplings of type JHH (n = 4-6) will be
detected.
19
The high resolution F NMR spectrum of trifluorochloromethane CF3Cl measured at lower
frequencies will appear as a slightly broadened singlet. Measurements at higher frequencies
resolve an overlap or clean separation of two singlets with intensity ratio of 3:1. Those peaks are
35 37
due to isotopomers CF3 Cl and CF3 Cl.
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F F F
35 37
F C Cl F C Cl F C Cl
F F F
19 1
Remember: F spins are more sensitive to isotope effects than H spins.
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8 Four-Spin Systems
8.1 Introduction
So far we have studied appearance and analysis of high resolution 1D NMR spectra in three
chapters:
1. The Trivial 1-Spin Case
A1
Topics Systems
Resonance frequency, spectral half width A1
Lorentzian line shape, integral A1
2. Three Different 2-Spin Systems
A2
AB AX
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Topics Systems
"First-order" spectra AX
"Second-order" spectra AB
Resonance frequencies, coupling constants, spectral

AX, AB, A2
Relation r
Manual analysis and simulation of spectra AX, AB, A2
3. Eight 3-Spin Systems of Practical Relevance
A3
A2 B AA´B AA´X A2 X
ABC ABX AMX
Topics Systems
First order spectra A4, A3X, A2X2, AMX2, AMRX
Magnetical equivalence, composite particles A2B, AB2, A2X, AX2
Isochronous spins AA´B, ABB´, AA´X, AXX´
X approximation and sub-spectral analysis ABX, AXY, AA´X, AXX´
Conjugated solutions ABX, AXY, AA´X, AXX´
ABX, AXY, AA´X, AXX´, ABC, AA´B,

Determination of signs from coupling constants
ABB´
Simplification of the spectral habitus by high field and

ABX, AXY
double resonance spectroscopy
Iteration of NMR parameters by computer programs ABC, AA´B, ABB´
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We will not continue with all 33 potential 4-spin problems but restrict to the 16 practically
relevant 4-spin systems (shown in a graphic below). We will pay attention to increasingly more
complex spectral patterns.
16 Practically Relevant 4-Spin Systems
A4
AB3 AX3
A 2 B2 [AB] 2 [AX] 2 A 2 X2
A 2 BC A 2 BX ABXY ABX 2 AMX2
ABCD ABCX ABMX AMRX
What We Will Learn in Subsequent Chapters
Topics Systems
A4, (A3X, AX3), A2X2, (AMX2, AM2X,

First order spectra
A2MX), AMRX
Magnetical equivalence,
(AB3, A3B), (AX3, A3X), A2B2, A2X2
accidental magnetical equivalence
Chemical equivalence [AB]2, [AX]2
(A2BX, AB2X), ABX2, (AMX2, AM2X,

X approximation and sub-spectral analysis
A2MX), ABMX, ABCX
Signs of coupling constants (A2BX, AB2X), ABX2, ABMX;
Simplification of the spectral habitus by

high field spectroscopy and (A2BX, AB2X), ABX2, ABMX, ABCX
double and triple resonance spectroscopy
Iteration of NMR parameters by computer programs TopSpin, DAISY
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Practically Relevant 4-Spin Systems are shown with some examples:
No. System Typical Compounds
15 AMRX Furylaldehyde
16 ABMX C6H2F2RR´
18 A2MX PH2F
19 ABXY C6H2F2RR´
20 ABCX CH2=CHF, CH2=CHPO3H2, C6H3FRR´
23 ABX2 C6H2F2RR´
24 AB2X C6H3FR2
27 [AX]2 C2H2F2, C6H2F2RR´

13
28 AXX´2 1,3,5-C6H3Cl3 C isotopomers
30 A2X2 CH2F2
31 AX3 CHF3, CH3F, CH3PCl2, CH3CR=CHR´
32 ABCD 1,2-C6H4RR´, 1,3-C6H4RR´,

34 ABC2 1,3-C6H4R2
37 [AB]2 1,2-C2H4R2, 1,4-C6H4RR´
40 A2B2 c-C4H4R2R´2
41 AB3 CH3OH, CH3SH, CH3CHR2, CH3CH=CRR´
43 [[A]2]2 1,4-C6H4R2
47 A4 CH4, CF4
The spectral habitus of systems like 15 AMRX, 16 ABMX, 18 A2MX, 30 A2X2, 31 AX3,
43 [[A]2]2, and 47 A4 is straight forward, and manual analysis is easy.
For systems like 20 ABCX, 23 ABX2, 24 AB2X, 28 AXX´2, 32 ABCD, 34 ABC2, and
41 AB3, we will use more elaborate techniques and introduce computer programs for simulation and
iteration of NMR spectra.
Particular attention will be paid to practically relevant spectral types like 19 ABXY,
27 [AX]2, 37 [AB]2, and 40 A2B2.
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8.2 The AMRX System – Spin System No. 15
The AMRX spectrum exhibits 32 lines of equal intensity. 8 lines are arranged symmetrically around
νA, νM, νR and νX. 6 repeated spacings are found, each 8 times in the total spectrum corresponding
to 6 coupling constants JAM, JAR, JAX, JMR, JMX, and JRX. Relative signs for coupling constants are not
accessible from direct AMRX analysis.
8.2.1 Practical Example 1: Furane Aldehyde
A classical example for AMRX is found in furane aldehyde:
H4 H3
C C
C C H1
H2 O C
Parameter Parameter Data

δ1 δA 9.693 [ppm]
δ2 δM 7.790 [ppm]
δ3 δR 7.316 [ppm]
δ4 δX 6.640 [ppm]
J12 JAM 0.8 [Hz]
J13 JAR 0 [Hz]
J14 JAX 0.4 [Hz]
J23 JMR 0.75 [Hz]
J24 JMX 1.7 [Hz]
J34 JRX 3.7 [Hz]
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1
A corresponding 500 MHz H NMR spectrum is shown below:
1
Expanded 500 MHz H NMR Spectrum of Furane Aldehyde
4848 4844
3896 3892
62 3660 3658 3656 36
3324 3322 3320 3318 3316

(Hz)
Figure 166 : AMRX spectrum. From top to bottom: A, M, R, and X parts.
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8.2.2 Practical Example 2: N-Methyl-Pyrolidone
Protons H3, H4, H5 and H6 from N-methyl-pyrolidone give rise to a neat AMRX system when
measured at 500 MHz. Spectra show remarkable solvent effects.
H4
H5 H3
H6 N O
CH3
3800 3600 3400 3200

(Hz)
1
Figure 167 : 500 MHz H NMR spectrum of N-methylpyrolidone in CD3COCD3
NMR Data for N-methylpyrolidone

Parameter [Hz] Spins Protons
ν1 3179.70 νR H3
ν2 3680.70 νM H4
ν3 3073.11 νX H5
ν4 3786.90 νA H6
J12 9.16 JMR H3H4
J13 1.37 JRX H3H5
J14 0.69 JAR H3H6
J23 6.58 JMX H4H5
J24 2.13 JAM H4H6
J34 6.76 JAX H5H6
HWB 0.3 HWB
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Transition Frequencies and Intensities. Peak Picking Frequencies.
Simulated Simulated Peak Picking

Line Frequency Intensity Frequency
1 3791.7170 0.9692 3791.72
2 3791.0258 0.9726 3791.02
3 3789.5867 1.0096 3789.58
4 3788.8956 1.0107 3788.89
5 3784.9582 0.9871 3784.96
6 3784.2670 0.9907 3784.26
7 3782.8279 1.0295 3782.83
8 3782.1368 1.0306 3782.14
9 3689.6836 0.9912 3689.68
10 3687.5534 0.9512 3687.55
11 3683.1042 1.0135 3683.11
12 3680.9739 0.9710 3680.96
13 3680.5240 1.0261 3680.53
14 3678.3938 0.9883 3678.39
15 3673.9446 1.0495 3673.94
16 3671.8144 1.0093 3671.81
17 3185.3231 1.0054 3185.33
18 3184.6319 1.0041 3184.63
19 3183.9523 1.0335 3183.95
20 3183.2611 1.0302 3183.27
21 3176.1635 0.9702 3176.16
22 3175.4724 0.9689 3175.48
23 3174.7928 0.9954 3174.80
24 3174.1016 0.9923 3174.10
25 3080.4263 1.0342 3080.43
26 3079.0555 1.0067 3079.06
27 3073.8468 1.0114 3073.79
28 3073.6675 1.0140 3073.72
29 3072.4761 0.9856 3072.41
30 3072.2967 0.9884 3072.41
31 3067.0880 0.9919 3067.09
32 3065.7172 0.9679 3065.72
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1
500 MHz H NMR Spectrum of N-methylpyrolidone in CD3COCD3
3800 3796 3792 3788 3784 3780 3776

(Hz)
3192 3188 3184 3180 3176 3172 3168

(Hz)
3692 3688 3684 3680 3676 3672 3668

(Hz)
3084 3080 3076 3072 3068 3064 3060

(Hz)
1
Figure 168 : Expanded 500 MHz H NMR spectrum of N-methylpyrolidone in acetone-d6. From top to
bottom: A, M, R, and X parts.
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Inspect the expansion for A, M, R, and X parts below. A minute ABCD character is visible. Work
through this AMRX case using frequencies listed above.
1
H NMR spectra of N-methylpyridone are remarkably solvent dependent and show some second
order character. Hence AMRX analysis was corrected by ABCD iterations using TopSpin / DAISY.
1
500 MHz H NMR Data of N-methylpyridone in CD3OD, CD3COCD3, CDCl3, C6D6
Parameter CD3OD CD3COCD3 CDCl3 C6D6

[Hz]
ν3 3272.36 C 3179.75 C 3287.77 C 3246.84 B
ν4 3764.02 B 3680.70 B 3666.54 A 3336.99 A
ν5 3188.95 D 3073.11 D 3078.03 D 2702.61 D
ν6 3819.92 A 3786.90 A 3644.55 B 3118.51 C

J34 9.08 9.17 9.16 9.18
J35 1.35 1.37 1.37 1.39
J36 0.68 0.69 0.69 0.69
J45 6.73 6.58 6.64 6.55
J46 2.05 2.13 2.12 2.15
J56 6.73 6.76 6.69 6.74
HWB3 0.80 0.87 0.81 0.69
HWB4 0.74 0.74 0.77 0.61
HWB5 0.81 0.83 0.81 0.66
HWB6 0.89 0.90 0.96 0.76
1
ABCD Iteration of spectra with TopSpin. Results from 500 MHz H NMR spectra of
N-methylpyridone in CD3OD, CD3COCD3, CDCl3, C6D6. All errors in ν, J and HWB lower than
± 0.0025 Hz.
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8.2.3 Practical Example 3: CBrClF-CBrF-CF=CBrF
FX
Br Br
C Br
Cl C C C
FA FM FR
Trans CBrClF-CBrF-CF=CBrF exists in erythro and threo forms each representing an AMRX
19
system for F NMR. Those AMRX spectra are perfectly first order, no ABCD character is
recognized. But here we meet another problem of spectral analysis: digital resolution in the
frequency axis. See the following spectrum characterized by a sweep width of 45000 Hz and 128 K
data points. The digital resolution is as low as 3 points/Hz. And this situation is met quite frequently
in heteronuclear NMR. Do NOT iterate such simple spectra by line shape based iterators like
TopSpin / DAISY and similar programs. Iteration might go astray. A frequency based iterator of
LAOCOON type would be better – but is NOT necessary for this situation. Manual AMRX analysis
suffices, using conveniently the tool Multiplet Analysis from TopSpin. Bear in mind, in this practical
example the NMR parameters will be determined with an accuracy not better than 0.3 Hz.
Isomer 1 Isomer 2
Parameter [Hz] [Hz]
νA -29968.6506 -29827.7500
νM -57290.7365 -57290.5000
νR -67012.4087 -67350.4167
νX -49313.6563 -49392.8333
JAM -26.86 -28.09
JAR 12.17 15.59
JAX 3.19 3.97
JMR -26.67 -27.14
JMX 53.24 53.34
JRX -132.37 -132.38
HWB 1 1
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It is recommended to acquire such spectra either with more data points (e. g. 512 K) or to acquire a
series of selected spectra with varied offsets and smaller sweep width.

Isomer 1 Isomer 2
1 -29947.5333 0.9985 -29803.9165 0.9984
2 -29950.7231 0.9989 -29807.8863 0.9988
3 -29959.7031 0.9992 -29819.5062 0.9992
4 -29962.8929 0.9995 -29823.4760 0.9996
5 -29974.3929 1.0005 -29832.0060 1.0004
6 -29977.5826 1.0008 -29835.9758 1.0008
7 -29986.5626 1.0011 -29847.5957 1.0012
8 -29989.7524 1.0015 -29851.5655 1.0016
9 -49218.9208 0.9861 -49297.6552 0.9862
10 -49222.1106 0.9857 -49301.6250 0.9857
11 -49272.1599 0.9993 -49350.9943 0.9995
12 -49275.3497 0.9990 -49354.9641 0.9991
13 -49351.2905 1.0009 -49430.0349 1.0008
14 -49354.4803 1.0005 -49434.0047 1.0003
15 -49404.5296 1.0144 -49483.3740 1.0144
16 -49407.7194 1.0141 -49487.3437 1.0140
17 -57237.4296 1.0049 -57236.2949 1.0051
18 -57264.0990 1.0105 -57263.4344 1.0105
19 -57264.2892 1.0029 -57264.3845 1.0030
20 -57290.6687 0.9916 -57289.6340 0.9916
21 -57290.9586 1.0085 -57291.5239 1.0085
22 -57317.3381 0.9970 -57316.7734 0.9969
23 -57317.5283 0.9897 -57317.7235 0.9896
24 -57344.1976 0.9951 -57344.8629 0.9949
25 -66927.0711 1.0106 -67263.1262 1.0105
26 -66939.2408 1.0099 -67278.7159 1.0097
27 -66953.7404 1.0050 -67290.2656 1.0051
28 -66965.9102 1.0044 -67305.8553 1.0042
29 -67059.4408 0.9956 -67395.5059 0.9957
30 -67071.6105 0.9949 -67411.0956 0.9949
31 -67086.1101 0.9901 -67422.6453 0.9904
32 -67098.2799 0.9895 -67438.2350 0.9896
Note: Threo and erythro forms are not assigned specifically to isomer 1 and isomer 2 of
CBrClF-CBrF-CF=CBrF.
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The Problem of Digital Resolution in Heteronuclear NMR
-30000 -40000 -50000 -60000

(Hz)
A M R X
-66920 -66960 -67000 -67040 -67080

(Hz)
X part
19
Figure 169 : Simulated F NMR spectrum of isomer 1 from CBrClF-CBrF-CF=CBrF. Upper: total.
Middle: X part. Lower: Line at lowest frequency for X part (outmost right) shown with x-scale = points.
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See low digital resolution: ca. 3 points [pts.] per half width. Not sufficient for good iterative
calculations using lines shape techniques. Increase number of data points per HWB!
Up to here we have studied homonuclear AMRX spectra. A multitude of heteronuclear AMRX

1 13 19
systems are found in organo phosphorus and organo fluorine chemistry involving nuclei H, C, F
31 13
and P NMR, e.g. in CHClFPCl2, high field NMR of the vinylic group in CH2=CH-O-P(O)(OCH3)2
1 2
and isomeric structures of derivatives from ortho- and meta-difluorobenzenes C6H2F2R R like
R1 R1 R1 R1
H F H R2 F H R2 H
H R2 H F H R2 H F
F F F F
or the heterocyclic compound 1
H H
H H H F
C C C C
C C C C
F S O H S O
1 2
This example gave rise to a classical ABMX spectrum when measured at 60 MHz as discussed by
R. A. Hoffmann, S. Forsén, B. Gestblom in “Analysis of NMR Spectra” as part of “Basic Principles
and Progress – Grundlagen und Fortschritte”, 6, 89-95 (1971). Springer-Verlag. New York,
Heidelberg, Berlin. (Editors: P. Diehl, E. Fluck, R. Kosfeld).
Read this interesting essay, which is a good piece of NMR spectral analysis. Find that the authors
misprinted the molecular structure. Formula 2 is consistent with NMR data, but not formula 1.
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8.2.4 Practical Example 4 and 5: Heteronuclear AMRX Systems
1 19
In 500 MHz H and 450 MHz F NMR spectra of 2-chloro-4,5-difluorobenzoic acid (1) and 4-chloro-
35 37
2,5-difluorobenzoic acid (2) the Cl/ Cl-isotope shift effect is visible for ortho- but not for meta-Cl,F-
pairs.
COOH COOH
H6 Cl H6 F2
F5 H3 F5 H3
F4 Cl
1 2
1 1 2 2a 2b
35 37
Cl Cl
A δH6 7.8866 A δH6 7.8005 7.8005

M δH3 7.5959 M δH3 7.5468 7.5468
R δF4 -130.9663 R δF2 -112.4750 -112.4750
X δF5 -139.1543 X δF5 -121.0606 -121.0620
5 5
AM JH3H6 0.37 AM JH3H6 0.38 0.38
4 4
AR JF4H6 8.56 AR JF2H6 6.24 6.24
3 3
AX JF5H6 10.83 AX JF5H6 9.19 9.19
3 3
MR JF4H3 10.30 MR J F2H3 9.74 9.74
4 4
MX JF5H3 7.09 MX JF5H3 5.92 5.93
3 5
RX JF4F5 -21.10 RX JF2F5 16.74 16.74
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2-Chloro-4,5-difluorobenzoic Acid 1
7.910 7.900 7.890 7.880 7.870 7.860
7.620 7.610 7.600 7.590 7.580 7.570

1
Figure 170 : 500 MHz H NMR spectrum of 2-chloro-4,5-difluorobenzoic acid 1. Upper: H6. Lower: H3.
-130.92 -130.94 -130.96 -130.98 -131.00
-139.12 -139.14 -139.16 -139.18 -139.20

19
Figure 171 : 450 MHz F NMR spectra of 2-chloro-4, 5-difluorobenzoic acid 1. Upper: F4. Lower: F5.
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4-Chloro-2,5-difluorobenzoic Acid 2
7.830 7.820 7.810 7.800 7.790 7.780 7.770
7.570 7.560 7.550 7.540 7.530 7.520

1
Figure 172 : 500 MHz H NMR spectra of 4-chloro-2,5-difluorobenzoic acid 2.. Upper: H6. Lower: H3.
-112.44 -112.46 -112.48 -112.50 -112.52
-121.02 -121.04 -121.06 -121.08 -121.10

19
Figure 173 : 450 MHz F NMR spectra of 4-chloro-4, 5-difluorobenzoic acid 1. Upper: F2. Lower: F5.
35 37
Observe the Cl/ Cl-Isotop shift effect in F5.
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8.2.5 Practical Example 6: CF2=CF-PCl2
Signs for couplings constants in AMRX of trifluorovinyldichlorophosphine
F F 1 3
C C
F PCl2 2 4
Parameters Sign Data Ref.
δ1 δF [ppm] 103.59 A
δ2 δF [ppm] 82.5 A
δ3 δF [ppm] 186.43 A
not found in
δ4 δP [ppm] - literature
±
2
J12 JFF [Hz] 39.1 B
±
3
J13 cis JFF [Hz] 32.0 B
±
3
J23 trans JFF [Hz] 123.4 B
2
J34 JPF [Hz] - 17.2 B
3
J24 cis JPF [Hz] + 85.7 B
3
J14 trans JPF [Hz] + 7.3 B
For details read:

a) H. Cowley, M. W. Taylor; J. Amer. Chem. Soc. 91, 1929 (1969)
b) H. Cowley, M. W. Taylor, J. Amer. Chem. Soc. 91, 1026 (1969)
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19
F NMR Spectrum of Trifluorovinyldichlorophosphine
17640 17580 17520 17460 1

(Hz)
9800 9760 9720 9680

(Hz)
7880 7840 7800 7760 7720 7680 7640

(Hz)
19
Figure 174 : F NMR spectrum of trifluorovinyldichlorophosphine. Upper: F3. Middle: F1. Lower: F2.
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Four-Spin Systems
8.2.6 Practical Example 7: AMRX and Chiral Discrimination
2+
Configurationally stable tris(bipyridyl)ruthenium(II) cation [Ru(bip)3] , a propeller type structure,
exists in two enantiomeric forms,
[Ru(bip)3]2+
H H H H
H H H H
H N N H
H N N H
Ru
H H H
H H
N N
H H
H H H H
1
which in achiral solvents gives rise to a single AMRX type H NMR spectrum showing minute ABCD
character:
8.4 8.2 8.0 7.8 7.6 7.4

(ppm)
1
Figure 175 : 400 MHz H NMR spectrum of [Ru(bip)3](ClO4)2 in CD2Cl2.
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Four-Spin Systems
For further discussions protons were indicated as shown below:
H1
H2
H4 H3
The simple appearance of an AMRX spectrum with low ABCD character indicates that inter-annular
long range HH-couplings are negligibly small or nil. Hence it is not necessary to deal with the more
complicated spin systems [AMRX]2 of the bipyridine ligand or even a hypothetic [[AMRX]2]3 of the
total complex cation. Here it suffices to consider half of the bipyridine ligand with its single AMRX
system.
The spectrum shown above corresponds to parameters:
Parameter Data [Hz]

ν1 3104
ν2 2996
ν3 3232
ν4 3388
J12 5.75
J13 1.33
J14 0
J23 7.96
J24 1.33
J34 8.16
HWB1 2
HWB2 1.5
HWB3 1.5
HWB4 2
Remarks: HWB: guessed. Other data: C. Ginglinger, private communication.

For details read:
a) J. Lacour, C. Ginglinger, F. Favarger, S. Torche-Haldimann; Chem. Comm. 1977, 2285-2286.
b) J. Lacour, C. Ginglinger, C. Grivet, G. Bernadinelli; Angew. Chem. Int. Ed. Engl. 36, 608-610,
(1997).
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Transition Frequencies and Intensities are Listed Below:

1 3392.8552 0.9438
2 3392.8531 0.9440
3 3391.5209 0.9515
4 3391.5188 0.9517
5 3384.6969 1.0493
6 3384.6948 1.0491
7 3383.3625 1.0553
8 3383.3605 1.0552
9 3240.6858 1.0097
10 3239.3496 1.0283
11 3232.7366 1.0745
12 3232.5275 0.9038
13 3231.4003 1.0965
14 3231.1913 0.9235
15 3224.5782 0.9703
16 3223.2420 0.9934
17 3107.6171 0.9526
18 3107.6150 0.9538
19 3106.2809 0.9401
20 3106.2788 0.9406
21 3101.8673 1.0680
22 3101.8652 1.0674
23 3100.5310 1.0394
24 3100.5290 1.0381
25 3003.3719 1.0939
26 3002.0375 1.0862
27 2997.6221 0.9802
28 2996.2878 0.9743
29 2995.4227 1.0202
30 2994.0883 1.0125
31 2989.6729 0.9193
32 2988.3385 0.9133
Solvent Effects
2+
Racemic mixtures of cationic [Ru(bip)3] in chiral solvents will form solvation diastereomers and
1
hence H NMR will show two individual sets of AMRX spectra.
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Shift Reagents
An efficient NMR chiral shift reagent is TRISPHAT, [NH(n-Bu)3][P(TCB)3], (another propeller type
-
structure). The anion [P(TCB)3] is shown below:
[P(TCB)3]-
Cl Cl Cl Cl
Cl O O Cl
Cl O P O Cl
O O
Cl Cl
Cl Cl
2+
which can be separated into an almost pure (+) enantiomeric form. Mixing [Ru(bip)3] and
[P(TCB)3] (1:1) in CD2Cl2 leads to the formation of diastereomeric ion pairs, (Λ -Λ and Λ -Λ ), as
- + - + +
1
deduced from the 400 MHz H NMR spectrum:
8.4 8.2 8.0 7.8 7.6 7.4

(ppm)
1
Figure 176 : 400 MHz H NMR of [Ru(bip)3](ClO4)2 and [NH(n-Bu)3][P(TCB)3] (1:1) in CD2Cl2.
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Four-Spin Systems
Simulate this spectrum with TopSpin / DAISY and its fragmentation technique.
Parameter Fragment 1 Fragment 2

ν1 3155.68 3084.80
ν2 2986.80 2947.60
ν3 3221.56 3187.96
ν3 3358.80 3367.60
Use identical data for coupling constants and spectral half widths as listed in the preceding table for
[Ru(bip)3](ClO4)2 in CD2Cl2. Results are given below:
Fragment 1 Fragment 2
1 3363.6706 0.9363 3372.4405 0.9511
2 3363.6683 0.9365 3372.4389 0.9512
3 3362.3344 0.9447 3371.1068 0.9580
4 3362.3319 0.9449 3371.1051 0.9581
5 3355.5128 1.0565 3364.2822 1.0425
6 3355.5104 1.0562 3364.2806 1.0424
7 3354.1769 1.0624 3362.9486 1.0483
8 3354.1744 1.0623 3362.9470 1.0483
9 3230.2333 1.0087 3196.6599 1.0011
10 3228.9006 1.0435 3195.3255 1.0241
11 3222.2831 1.0713 3188.7078 1.0645
12 3222.0755 0.8872 3188.5016 0.9091
13 3220.9503 1.1140 3187.3735 1.0918
14 3220.7427 0.9252 3187.1673 0.9334
15 3214.1256 0.9516 3180.5497 0.9735
16 3212.7927 0.9986 3179.2153 1.0025
17 3159.2651 0.9814 3088.3989 0.9671
18 3159.2628 0.9833 3088.3973 0.9682
19 3157.9324 0.9500 3087.0646 0.9485
20 3157.9301 0.9490 3087.0630 0.9486
21 3153.5143 1.0575 3082.6489 1.0582
22 3153.5118 1.0590 3082.6472 1.0583
23 3152.1815 1.0111 3081.3145 1.0262
24 3152.1790 1.0086 3081.3128 1.0249
25 2994.2010 1.0735 2954.9907 1.0807
26 2992.8648 1.0659 2953.6570 1.0738
27 2988.4502 1.0014 2949.2407 0.9917
28 2987.1138 0.9946 2947.9069 0.9860
29 2986.2507 1.0022 2947.0387 1.0101
30 2984.9149 0.9946 2945.7050 1.0030
31 2980.4999 0.9373 2941.2886 0.9302
32 2979.1639 0.9305 2939.9549 0.9244
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8.3 The ABMX and Related AMNX, AMXY Systems

– Spin System No. 16
8.3.1 Practical Example 1: The ABMX Case of 5-Fluoro-3-thiolene-2-one
This section is meant to be a reference to a didactically useful - but old - case: The ABCX system in
1 19
5-fluoro-3-thiolene-2-one. Analysis of 60 MHz H and 56.4 MHz F NMR spectra. Approximation as
ABMX to AMRX Systems. Described by R. A. Hoffmann, S. Forsén, B. Gestblom; NMR Basic
Principles and Progress - Grundlagen und Fortschritte, Vol. 5. 87-95, Springer Verlag, New York,
Heidelberg, Berlin, 1971. (Editors: P. Diehl, E. Fluck and R. Kosfeld).
Mono-fluoro-thiolene-ones C4H3FOS may exist in 6 different structures:
H H H
H H F H H F
F S O H S O H S O
1 2 3
H H F H H F
H S O H S O H S O
F H H
4 5 6
While structures 1, 2, 5 and 6 give rise to AM2X to AB2X spectra, for compounds 3 and 4 AMRX to
ABMX spectra are expected.
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1 19
In the following chapter, we will study the AMRX system in H and F NMR spectra from 4 which is
5-fluoro-3-thiolene-2-one.
1 19
60 MHz H and 56.4 MHz F NMR Data from 5-Fluoro-3-thiolene-2-one 4
Parameter Type Data [Hz]
ν1 νH 435.81
ν2 νH 404.81
ν3 νH 364.09
ν4 νF 30.25
3
J12 JHH 2.77
4
J13 JHH 6.17
3
J23 JHH -0.81
3
J14 JHH 4.05
2
J24 JHH 52.47
2
J34 JFH -2.06
1 19
60 MHz H and 56.4 MHz F NMR data from 5-fluoro-3-thiolene-2-one 4
a)
δH and νH vs. int. TMS. b) δF and νF vs. int. C6F6.
19
56.4 MHz F NMR Spectrum
60 50 40 30 20 10 0
(Hz)
19
Figure 177 : Simulated 56.4 MHz F NMR spectrum. Total.
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Four-Spin Systems
19
Expanded 56.4 MHz F NMR Spectrum
*
*
*
*
66 64 62 60 58 56 54 52 50 48
(Hz)
*
*
*
*
10 8 6 4 2 0 -2 -4 -6
(Hz)
19
Figure 178 : Simulated 56.4 MHz F NMR spectrum expanded. Upper: low field part. Lower: high field
part.
From two sub-spectra of type AX and two sub-spectra of type ABX in the Fluorine NMR spectrum
(X) we can expect two different proton sub-spectra: with properties close to ABX and AMX types.
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And this is true, as we will see below.
1
60 MHz H NMR Spectrum
7.4 7.2 7.0 6.8 6.6 6.4 6.2 6.0

(ppm)
1
Figure 179 : Simulated 60 MHz H NMR spectrum. Total.
444 440 436 432 428 424

(Hz)
380 376 372 368 364 360 356

(Hz)
1
Figure 180 : Simulated 60 MHz H NMR spectrum, expanded: Upper: low field part. Lower: high field part.
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1
7.4 7.2 7.0 6.8 6.6 6.4 6.2 6.0

(ppm)
7.4 7.2 7.0 6.8 6.6 6.4 6.2 6.0

(ppm)
7.4 7.2 7.0 6.8 6.6 6.4 6.2 6.0

(ppm)
1
Figure 181 : Upper: total simulated 60 MHz H NMR spectrum. Middle: sub-spectrum for mF = +1/2.
19
Lower: sub-spectrum for mF = -1/2. See comments on F NMR spectrum above.
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1
446 444 442 440 438 436 434 432 430 428 426 424
(Hz)
374 372 370 368 366 364 362 360 358 356 354 352
(Hz)
1
Figure 182 : Simulated 60 MHz H NMR sub-spectrum for mF = +1/2. Upper: low field part. Lower: high
field part.
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1
444 442 440 438 436 434 432 430 428 426 424 422
(Hz)
382 380 378 376 374 372 370 368 366 364 362 360
(Hz)
1
Figure 183 : Simulated 60 MHz H NMR sub-spectrum for mF = -1/2. Upper: low field part. Lower: high
field part.
1 19
60 MHz H{ F} NMR Spectrum
7.4 7.2 7.0 6.8 6.6 6.4 6.2 6.0

(ppm)
1 19
Figure 184 : Simulated fluorine decoupled 60 MHz H{ F} NMR spectrum.
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The paper of R. A. Hoffmann, S. Forsén and B. Gestblom may serve as an introduction to the sub-
spectral analysis of AMRX spin systems. Possibly by misprint the authors quoted erroneously
structure 1 for 5-fluoro-3-thiolene-2-one - which is excluded by NMR and symmetry considerations.
Problems:
Why are those data characteristic for 5-fluoro-3-thiolene-2-one 4 and NOT for
5-fluoro-4-thiolene-2-one 3? Find arguments from chemical shift considerations. Attribute spins H1,
1 19
H2, H3, F4 to the three H atoms and the F atom in 5-fluoro-3-thiolene-2-one 4.
Advantage of High Field Spectroscopy: 500 MHz 1H and 470 MHz 19F NMR Spectra
Increasing the field strength simplifies the spectrum. At 500 MHz a primitive AMRX system is
observed. Analysis is straight forward.
280 270 260 250 240 230

(Hz)
19
Figure 185 : Simulated 470 MHz F NMR spectrum
7.2 7.0 6.8 6.6 6.4 6.2 6.0

(ppm)
1
Figure 186 : Simulated 500 MHz H NMR spectrum.
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1
Simulated Fluorine 500 MHz H NMR Spectrum.
3640 3620 3600

(Hz)
3400 3380 3360

(Hz)
3060 3040 3020

(Hz)
1
Figure 187 : Simulated fluorine 500 MHz H NMR spectrum. Upper: low field part. Middle: center part.
Lower: high field part.
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8.3.2 Practical Example 2: The Pair of Isomers
H H H H
Ph C C COOEt EtOOC C C Ph
F H F H
1 β-Phenyl-β-fluoro-propionic acid ethylester

2 β-Phenyl-α-fluoro-propionic acid ethylester
1 19
give rise to AMNX spectra which were analyzed by 270 MHz H NMR and 94 MHz F NMR studies.
The proton and the fluorine from -CHF- form the A and the X parts. The pair of protons from the
geminal -CH2- group is nonequivalent (due to the neighboring chiral center) and responsible for the
MN part. Inspect the simulated spectra and then work out the AMNX case for isomer 2.
1
270 MHz H NMR Spectrum of Isomer 1
6.0 5.5 5.0 4.5 4.0 3.5 3.0

(ppm)
1
Figure 188 : 270 MHz H NMR spectrum of isomer 1: the AMN part
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Four-Spin Systems
1660 1640 1620 1600 1580 1560 1540

(Hz)
1
Figure 189 : 270 MHz H NMR spectrum of isomer 1: the A part
840 820 800 780 760 740 720

(Hz)
1
Figure 190 : 270 MHz H NMR spectrum of isomer 1: the MN part
-44220 -44250 -44280

(Hz)
19
Figure 191 : 254 MHz F NMR spectrum of isomer 1: the X part
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1
270 MHz H NMR Spectrum of Isomer 2
6.0 5.5 5.0 4.5 4.0 3.5 3.0

(ppm)
1
Figure 192 : 270 MHz H NMR spectrum of isomer 2: the AMN part
1400 1380 1360 1340 1320

(Hz)
1
Figure 193 : 270 MHz H NMR spectrum of isomer 2: the A part
880 860 840 820

(Hz)
1
Figure 194 : 270 MHz H NMR spectrum of isomer 2: the MN part
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Four-Spin Systems
-48390 -48420 -48450 -48480

(Hz)
19
Figure 195 : 254 MHz F NMR spectrum of isomer 2: the X part
Spectra were Simulated Using the Data Listed Below
Isomer 1 Isomer 2
Parameter [Hz] [Hz]
νA 1593.00 1363.50
νM 812.70 864.00
νN 747.90 839.70
νX -44248.18 -48439.30
JAM 9.0 4.5
JAN 4.5 7.5
JAX 46.0 47.5
JMN -15.5 -14.5
JMX 15.5 26.5
JNX 30.5 24.5
HWB 0.3 0.3
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Transition Frequencies and Intensities for Isomers 1 and 2 are Listed in the Following Table:
Isomer 1 Isomer 1 Isomer 2 Isomer 2

1 1622.7836 0.9835 1393.2880 0.9773
2 1618.1994 0.9940 1388.6057 0.9946
3 1613.8682 1.0056 1385.9707 1.0038
4 1609.2840 1.0167 1381.2884 1.0230
5 1576.7847 0.9830 1345.7895 0.9764
6 1572.2298 0.9936 1341.0811 0.9943
7 1567.8400 1.0061 1338.4985 1.0037
8 1563.2851 1.0172 1333.7901 1.0240
9 833.6649 0.7576 888.7659 0.4841
10 824.7495 0.7194 884.0837 0.5199
11 818.1652 1.2648 874.2664 1.5342
12 817.9694 0.8068 869.5841 1.4620
13 809.2498 1.2582 862.4207 0.4504
14 809.0247 0.7736 860.8997 1.5389
15 802.4697 1.2166 857.7122 0.4911
16 793.5250 1.2030 853.5824 1.4571
17 772.1555 1.2591 847.9212 1.5688
18 767.5712 1.2639 846.4001 0.4884
19 756.6558 0.7517 843.2128 1.4898
20 752.0716 0.7253 839.0829 0.5154
21 741.8499 1.2105 836.2433 1.5736
22 737.2949 1.2091 828.9522 1.4848
23 726.3502 0.8004 821.7438 0.4549
24 721.7953 0.7799 814.4527 0.4865
25 -44202.1762 1.0000 -48390.0546 1.0000
26 -44217.8717 0.9994 -48414.7109 0.9996
27 -44232.4818 0.9994 -48416.3998 0.9996
28 -44248.1751 1.0000 -48437.5530 1.0000
29 -44248.1773 1.0000 -48441.0562 1.0000
30 -44263.8999 0.9992 -48462.1832 0.9997
31 -44278.4514 0.9992 -48463.9244 0.9997
32 -44294.1762 1.0000 -48488.5546 1.0000
Red: A-lines, Green: X-lines, Maroon: MN-lines not yet specified, see below.
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Spectral Analysis of AMNX from Isomer 2
The A and X Parts

We expect the A part of an AMN system doubled by splitting with JAX, hence a maximum of 12 lines.
Analogously we expect the X part of an MNX system doubled by splitting with JAX, hence again a
maximum of 12 lines. But the A and X parts are simple 8-line patterns which can be analyzed like A
and X parts of an AMRX system. Repeated spacings show the absolute values of JAM, JAN, JAX in the
A part and JAX, JMX, JNX in the X part. This indicates a weak coupling between spins M and N.
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The MN Part - Decomposition into mn Sub-spectra
Four mn sub-spectra are expected originating from spin states αAαX, βAαX, αAβX, and β AβX.
880 860 840 820

(Hz)
880 860 840 820

(Hz)
880 860 840 820

(Hz)
880 860 840 820

(Hz)
Figure 196 : Four mn sub-spectra corresponding to spin states αAαX, βAαX, αAβX, and βAβX.
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Four-Spin Systems
Effective Larmor Frequencies are Given by:
1 1 1 1
[1] νm1 =νM + JAM + JMX [5] νn1 =νN + JAN + JNX
2 2 2 2
1 1 1 1
[2] νm2 =νM − JAM + JMX [6] νn2 =νN − JAN + JNX
2 2 2 2
1 1 1 1
[3] νm3 =νM + JAM − JMX [7] νn3 =νN + JAN − JNX
2 2 2 2
1 1 1 1
[4] νm4 =νM − JAM − JMX [8] νn4 =νN − JAN − JNX
2 2 2 2
Identify the four characteristic mn sub-spectra. Remember the symmetry of a general AB spectrum
and the “roof effect” So : Si = Ii:Io.
1 2 3 4 56 7 8 9 10 11 12 13 14 15 16
Figure 197 : The MN part divided into four mn sub-spectra
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List of Transitions Frequencies and Intensities Used in the Figure Above

1 888.7659 0.4841
2 884.0837 0.5199
3 874.2664 1.5342
4 869.5841 1.4620
5 862.4207 0.4504
6 860.8997 1.5389
7 857.7122 0.4911
8 853.5824 1.4571
9 847.9212 1.5688
10 846.4001 0.4884
11 843.2128 1.4898
12 839.0829 0.5154
13 836.2433 1.5736
14 828.9522 1.4848
15 821.7438 0.4549
16 814.4527 0.4865
AB Type Analysis for mn Sub-spectra: Numerical Results for Defining νmi > νni
i νmi νni
[Hz] [Hz]
1 879.5 855.7
2 875.0 848.2
3 853.0 831.2
4 848.5 823.7
Repeated differences between νmi lead to coupling constants JAM, JMX.
Repeated differences between νni lead to coupling constants JAN, JNX.
Since all signs of JAM, JAN, JMX, JNX ( JHH and JFH) are positive defining νmi > νni is justified.
3 3
But if no information on signs for coupling constants are available prior to analysis, the situation is
more complex. How many conjugate solutions can be constructed from analyzing the MN part only?
Check conjugate solution with frequencies and intensities seen in the A and X parts.
Remember: HH-COSY45 spectra will yield relative signs of coupling constants, see also the
chapters above.
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Intramolecular Rotation and Spin Assignments
Rotameric Forms of Isomers 1 and 2

F F F
R2 H2 H2 H3 H3 R2
H1 R1 H1 R1 H1 R1
H3 R2 H2
I II III
Rotameric Forms of Isomers 1 and 2

1 2
Isomer R R I II III
1 Ph COOEt rel. pop. 6 2 2
2 COOEt Ph rel. pop. 4 2 4
rel. pop. = relative population of rotamer
3 3
The final spin assignment based upon KARPLUS type relations J(trans) > J(gauche) for coupling
3 3
constants JHH and JFH
Isomer JAM JAN JMX JNX

3 3 3 3
JHH JHH JFH JFH
1 9.0 4.5 15.5 30.5
2 4.5 7.5 26.5 24.5
hence
1 2
Isomer R R H1 H2 H3
1 Ph COOEt HA HM HN
2 COOEt Ph HA HN HM
Observe the interchange of resonance frequencies for H2 and H3 in isomer 1 and 2.
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For details read: S. Hamman, C. Beguin, C. Churine, C. Luu-Duc; Org. Magn. Res. 21, 361-366
3 3 3
(1983). The dependency of coupling constants JHH(trans), JHH(gauche), JFH(trans), and
3
JFH(gauche) on substituent electro negativities and dihedral angles is described in this paper.
Simplify your problems with double resonance: decoupling the X-nucleus
1400 1380 1360 1340 1320

(Hz)
1 19
Figure 198 : 270 MHz H{ F} NMR spectrum – the A part
880 860 840 820

(Hz)
1 19
Figure 199 : 270 MHz H{ F} NMR spectrum - the MN part
Following the techniques shown in the chapter for ABX analysis, parameters νA, νM, νN, JMN, JAM,
and JAN are extracted efficiently.
1 1
Decoupling the A-nucleus is more difficult since H{ H} double resonance is required. This technique
is skipped here.
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8.4 The A2MX and Related AM2X, AMX2 Systems

F H
Cl Cl F Cl Cl
Cl
H C P
Cl
H H F F F
F H
A2MX AM2X AMX2
A hypothetical A2MX case using NMR data
Parameter Data [Hz]

νA 40
νM 0
νX -40
JAM 6
JAX 4
JMX 2
is shown in the following graphic:
50 40 30 20 10 0 -10 -20 -30 -40 -50

[Hz]
A2 M X
Figure 200 : Simulation of an A2MX spectrum.
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Four-Spin Systems
The A2MX spectrum consists of a total of 16 lines: 4 A-, 6 M-, and 6 X-lines. 3 repeated spacings
are found; each 6 times, corresponding to absolute values of JAM, JAX, and JMX.
8.4.1 Practical Example 1: Homonuclear AMX2
AMX2 in 500 MHz H NMR Spectra of ∆ - and ∆ -pyrrolidine-2-one in D2O

1 3 4
HM HA HX HM
HX
C C C C
HX
O C C O C C HA
HX
N N
D D
1 2
Parameter ∆3- pyrrolidine-2-one ∆4-pyrrolidine-2-one

1 1 2 2
δA 7.44 δH 6.56 δH
δM 6.16 δH 5.46 δH
δX 4.17 δH 3.12 δH
3 3
JAM 5.75 JHH 4.9 JHH
3 4
JAX 1.70 JHH 2.3 JHH
4 3
JMX 1.90 JHH 2.4 JHH
For details read: R. Mondelli, C. Bocchi, G. P. Gardini and L. Chierici; Org. Magn. Res. 3, 7-22
(1971).
Work through the following AMX2 spectra.
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500 MHz H NMR Spectrum of ∆ -pyrrolidin-2-one

1 3
3724 3720 3716 3

(Hz)
Figure 201 : A part from 500 MHz H NMR spectrum of ∆ -pyrrolidin-2-one

1 3
3084 3080 3076 3

(Hz)
Figure 202 : M part from 500 MHz H NMR spectrum of ∆ -pyrrolidin-2-one

1 3
2088 2084 2080

(Hz)
Figure 203 : X2 part from 500 MHz H NMR spectrum of ∆ -pyrrolidin-2-one

1 3
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500 MHz H NMR Spectrum of ∆ -pyrrolidin-2-one

1 4
3284 3280 3276 3

(Hz)
Figure 204 : A part from 500 MHz H NMR spectrum of ∆ -pyrrolidin-2-one

1 4
2736 2732 2728 2724

(Hz)
Figure 205 : M part from 500 MHz H NMR spectrum of ∆ -pyrrolidin-2-one

1 4
1564 1560 1556

(Hz)
Figure 206 : X2 part from 500 MHz H NMR spectrum of ∆ -pyrrolidin-2-one

1 4
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8.4.2 Practical Example 2: Heteronuclear AM2X in CCl2=CH-CH2-P(O)(OEt)2
Parameter Data
δH(CH) δA 5.08 [ppm]
δH(CH2) δM 2.44 [ppm]
δP δX 25* [ppm]
3
JHH JAM 8 [Hz]
3
JPH JAX 6.5 [Hz]
2
JPH JMX -22 [Hz]
*) by definition, not accurate
1
500 MHz H NMR Spectra of A and M2 Parts
2550 2540 2530

(Hz)
1
Figure 207 : A part: =CH- from 500 MHz H NMR spectrum of CCl2=CH-CH2-P(O)(OEt)2
1230 1220 1210

(Hz)
1
Figure 208 : M2 part: -CH2- from 500 MHz H NMR spectrum of CCl2=CH-CH2-P(O)(OEt)2
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8.5 The ABXY System – Spin System No. 19
8.5.1 200 MHz 1H{31P} NMR Spectrum of 2-Methoxy-1-oxa-3-thia-phospholane
Phospholanes have attracted multifaceted attention in preparative organo phosphorous chemistry.

1
In addition those compounds give rise to interesting and didactically useful H NMR spectra.
Consider the following structures 1 to 3:
CH2 CH2 CH2 CH2 CH2 CH2
O O S S O S
-CH2-CH2-
P P P
°° °° °°
OCH3 OCH3 OCH3
1 2 3
1H NMR [AB]2X [AB]2X ABMNX
1H{31P} NMR [AB]2 [AB]2 ABMN = ABXY
The 2-methoxy-1,3-dioxa- and the 2-methoxy-1,3-dithiaphospholanes 1 and 2 are characterized

1
by symmetric [AB]2X H NMR spectra (of class 4).
1 31
Decoupling the phosphorous by H{ P} leads to the parent [AB]2 system. This system will be dealt
with in details in chapter 8.15.
Here we will concentrate on the asymmetrical 2-methoxy-1-oxa-3-thia-phospholane 3 where the
total 1H NMR spectrum ABMNX is decoupled by 1H{ P} NMR to ABMN, approximating the ABXY
31
situation.
2-Methoxy-1-oxa-3-thia-phospholane is characterized by a chiral center at phosphorous which
induces non-equivalence effects within and between both pairs of protons from the
-CH2-CH2- fragment. Nearest neighbors oxygen and sulphur induce specific shift ranges for each of
the -CH2- group. Hence four anisochronous protons in -CH2-CH2- are found forming the ABXY
system. Corresponding NMR parameters are listed in the following table:
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Four-Spin Systems
1 31
200 MHz H{ P} NMR Data for 2-Methoxy-1-oxa-3-thia-phospholane
Parameters [Hz]
νA 910.00
νB 844.00
νX 610.00
νY 586.00
JAB -9.35
JAX 5.99
JAY 6.12
JBX 6.88
JBY 6.02
JXY -11.09
1 31
The 200 MHz H{ P} NMR spectrum of 2-methoxy-1-oxa-3-thia-phospholane is shown in 2 parts:
920 910 900 890 880 870 860 850 840 830
[Hz]
Figure 209 : AB part (the -O-CH2- group).
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Four-Spin Systems
650 640 630 620 610 600 590 580 570 560 550
[Hz]
Figure 210 : XY part (the -CH2-S- group).
1 31
200 MHz H{ P} NMR Transition Frequencies and Intensities
XY Part AB Part
573.057 0.548 832.646 0.911
579.141 0.589 838.731 0.864
579.202 0.570 839.435 0.853
534.144 1.367 841.992 1.196
585.287 0.614 845.519 0.811
590.227 1.419 848.076 1.143
590.289 1.419 848.782 1.135
596.373 1.473 854.866 1.086
599.210 1.363 899.651 1.184
605.195 1.415 905.634 1.140
606.000 1.422 905.797 1.140
610.297 0.541 908.997 0.895
611.983 1.478 911.780 1.098
616.281 0.565 914.981 0.858
617.086 0.594 915.142 0.861
623.070 0.622 921.127 0.825
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Four-Spin Systems
In order to handle the ABMN case as ABXY system it is useful to introduce linear combinations of
coupling constants as shown below:
[1] N=
1 JAX + JAY [5] L
=1 JAX − JAY
[2] N=
2 JBX + JBY [6] L=
2 JBX − JBY
[3] N=
3 JAX + JBX [7] L=
3 JAX − JBX
[4] N=
4 JAY + JBY [8] L=
4 JAY − JBY
N and L parameters follow relations:
[9] N1 + N2 = N3 + N4 [12] L1 + L 4 = L 2 + L3
[10] N1 − N3 = N4 − N2 [13] L1 − L 2 = L3 − L 4
[11] N1 − N4 = N3 − N2 [14] L1 − L3 = L 2 − L 4
4 characteristic coupling constants JAX, JAY, JBX, and JBY are vicinal 3JHH with numerical values [Hz]
shown for this example below:
JAX = 5.99 N1 = 12.11 L1 = - 0.13
JAY = 6.12 N2 = 12.90 L2 = + 0.86
JBX = 6.88 N3 = 12.87 L3 = - 0.89
JBY = 6.02 N4 = 12.14 L4 = + 0.10
The ABXY system is characterized by a total of 32 transitions, 8 for each nucleus A, B, X, and Y.
Half of those transitions, 16 lines, can be described by explicit algebraic expressions for frequencies
and intensities as well. The origin of the remaining 16 transitions is more complex, and no explicit
algebraic expressions can be formulated for frequencies and intensities. But it is possible to make
educated simplifications, analogous to the analysis ABMX or AMXY spectra (handled above under
chapter 8.3).
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The total ABXY spectrum is divided into the following parts:
The N-lines system - lines which have explicit analytical solutions

1. The AB part: spin states of X and Y are αα or ββ.
2. The XY part: spin states of A and B are αα or ββ.
The L-lines system - lines which do not have explicit analytical solutions
3. The AB part: spin states of X and Y are αβ or βα.
4. The XY part: spin states of A and B are αβ or βα.
Analysis of N-line systems leads to resonance frequencies νA, νB, νX, νY, to N parameters N1,
N2, N3, N4, and further to coupling constants JAB and JXY resp..
Approximated data for L1, L2, L3, and L4 are extracted from the analysis of the L-line systems.
Combining the N und L parameters yields JAX, JAY, JBX, and JBY, which will serve as starting
values for iterative calculations using programs of LAOCOON type or favorably TopSpin / DAISY.
Following the Practical Route of Analysis
1. The AB part: spin states of X and Y are αα or ββ.
Two sub-spectra are observed with effective Larmor frequencies:
1 1
[15] ν a1 =ν A + (JAX + JAY ) =ν A + N1
2 2
1 1
[16] νb1 =νB + (JBX + JBY ) =νB + N2
2 2
1 1
[17] ν a4 =ν A − (JAX + JAY ) =ν A − N1
2 2
1 1
[18] νb4 =νB − (JBX + JBY ) =νB − N2
2 2
and the coupling constant JAB. Please inspect the spectrum and table given above and reanalyze:
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Four-Spin Systems
1
[19] ν=
A ( ν a + ν a4 )
2 1
1
[20] ν=
B ( ν b + ν b4 )
2 1
[21] N1 = (ν a1 − ν a4 )
[22] N2 = (νb1 − νb4 )
AB Part: Spin States of X and Y are αα or ββ.

νA νB
νa1 νa4 νb1 νb4

N1 N2
JAB JAB JAB JAB
925. 915. 905. 895. 885. 875 865. 855. 845. 835. 825.
[ Hz ]
Figure 211 : AB part: spin states of X and Y are αα or ββ.
2. XY Part: Spin States of A and B are αα or ββ.
The above given equations are modified analogously for the XY part. The effective Larmor
frequencies follow from:
1 1
[23] ν x1 =ν X + (JAX + JBX ) =ν X + N3
2 2
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Four-Spin Systems
1 1
[24] ν y1 =ν Y + (JAY + JBY ) =ν Y + N4
2 2
1 1
[25] ν x4 =ν X − (JAX + JBX ) =ν X − N3
2 2
1 1
[26] ν y4 =ν Y − (JAY + JBY ) =ν Y − N4
2 2
The corresponding coupling constant is JXY.
Reanalyze the spectrum:
1
[27] ν=
X (ν x + ν x4 )
2 1
1
[28] ν=
Y (ν y + ν y4 )
2 1
[29] N3 = (ν x1 − ν x4 )
[30] N4 = (ν y1 − ν y4 )
The XY Part: Spin States of A and B are αα or ββ.

νx νy
νx1 νx4 νy1 νy4

N3 N4
Jxy Jxy JXY JXY
650. 640. 630. 620. 610. 600 590. 580. 570. 560. 550.
[ Hz ]
Figure 212 : XY part: spin states of A and B are αα or ββ.
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Four-Spin Systems
3. AB Part: Spin States of X and Y are αβ or βα.
Since we are unable to analyze this part of ABXY accurately we will approximate it by application of
ABMX-rules, see chapter 8.3. In order to obtain approximated parameters, the following equations
for effective Larmor frequencies will be used:
1 1
[31] ν a2 =ν A + (JAX − JAY ) =ν A + L1
2 2
1 1
[32] νb2 =νB + (JBX − JBY ) =νB + L 2
2 2
1 1
[33] ν a3 =ν A − (JAX − JAY ) =ν A − L1
2 2
1 1
[34] νb3 =νB − (JBX − JBY ) =νB − L 2
2 2
which will be used in more or less distorted ab type sub-spectra together with the coupling constants
constant JAB.
Please inspect the example given in this section. You will find that this is a case of low distortion and
hence the observed ab type sub-spectra look very much like normal undisturbed cases. Find by re-
analysis:
[35] L1 = (νa2 − ν a3 )
[36] L 2 = (νb2 − νb3 )
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AB Part: Spin States of X and Y are αβ or βα.
JAB
JAB
∼νB
JAB
JAB
925. 915. 905. 895. 885. 875 865. 855. 845. 835. 825.
[ Hz ]
Figure 213 : AB part: spin states of X and Y are αβ or βα.
4. XY Part: Spin States of A and B are αβ or βα.
Using the ABXY approximation expressions for effective Larmor frequencies are obtained:
1 1
[37] ν x2 =ν X + (JAX − JBX ) =ν A + L3
2 2
1 1
[38] ν y2 =ν Y + (JAY − JBY ) =νB + L 4
2 2
1 1
[39] ν x3 =ν X − (JAX − JBX ) =ν A − L3
2 2
1 1
[40] ν y3 =ν Y − (JAY − JBY ) =νB − L 4
2 2
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Coupling constant in those “distorted ab type sub-spectra“ is JXY.
By inspection of the spectrum shown below we hardly detect any distortions. Obviously this is a
lucky case of ABXY which allows a smooth direct analysis. The missing parameters of this ABXY
system are found by:
[41] L3 = (ν x2 − ν x3 ) [42] L 4 = (ν y2 − ν y3 )
XY Part: Spin States of A and B are αβ or βα.
JXY
JXY
∼νX
JXY
JXY
650 640. 630. 620. 610 600 590. 580. 570. 560. 550.
[ Hz ]
Figure 214 : XY part: spin states of A and B are αβ or βα.
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Four-Spin Systems
Results from the Approximated ABXY Analysis:
Direct analysis of the ABXY spectrums yields
Accurate Data for
resonance frequencies νA νB νX νY
coupling constants JAB JXY
N parameters N1 N2 N3 N4
Approximated Data for
L parameters L 1 
L 2

L 3

L 4
After marking the approximated parameters by the symbol ~ , final equations can be written down,
to obtain the missing (still approximated) coupling constants:
1 1
[43] J AX = (N1 + L 1) = (N3 + L 3 )
2 2
1 1
[44] J AY = (N1 − L 1) = (N3 − L 3 )
2 2
1 1
[45] J BX = (N2 + L 2 ) = (N4 + L 4 )
2 2
1 1
[46] J BY = (N2 − L 2 ) = (N4 − L 4 )
2 2
The Final Solution
Start a spectral simulation with parameters νA, νB, νX, νY, JAB, JXY, JAX, JAY, JBX, and JBY.
Assign all 32 lines for ABXY iteration with one of the LAOCOON type programs or more favorably
directly without line assignment using TopSpin / DAISY.
Results will be the optimized values for ν A, νB, νX, νY, JAB, JXY, JAX, JAY, JBX, and JBY.
LAOCOON is useful for small spin systems but has some disadvantages. Fitting the frequencies
from experimental Lorentzian peak maxima to calculated transition frequencies may induce minor
errors. Better would be to perform a deconvolution and fit the deconvoluted frequencies to
theoretical ones. This problem is overcome by Laatikainen´s program PERCH using integral
transforms.
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Four-Spin Systems
But it is more convenient to start TopSpin / DAISY with automated analysis based upon line
shape evaluation. TopSpin / DAISY is intensity-fitting.
You are well prepared when you keep all three types of iterators ready for use in your NMR
armory.
Quite a few difficult spectra exist, which resist iteration either upon frequencies or
intensities. But no explicit expressions are known to predict the iterability of NMR spectra.
8.5.2 ABXY System in a CH2-CH2 Fragment of a P-Chiral Compound
31 1 31
The P-decoupled H{ P} NMR spectrum of the -CH2-CH2- fragment of 2-(P-methyl-P-chloro-
phosphinyl)-propionylchloride represents an ABXY system.
This compound is a precursor for polycondensates and flame retardants and in addition provides an
interesting model for ABMNX and ABXY spectra.
Phosphorous will be decoupled at 161.92 MHz while protons resonate at 400 MHz.
4
A long-range coupling constant JHH (-CH2-P-CH3) is not resolved but gives rise to line broadening
in the CH2-P unit, which will be neglected during the course of spectral analysis and simulation
presented here.
5
In addition the long range coupling JHH (-CH2-CH2-P- CH3) is not detected.
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Four-Spin Systems
3
Inspect the JHH data and derive, that the trans-rotamer of the -CH2-CH2- skeleton is the most
favored conformer. Free rotation around C-P is assumed.
1 31
400 MHz H{ P} NMR of Cl(O)C-CH2-CH2-P(CH3)(O)Cl (30% in CDCl3)
The ABXY Spectrum
1400 1390 1380 1370 1360 1350 1340 1330 1320 1310 1300
[Hz]
Figure 215 : The AB part of ABXY.
080 1070 1060 1050 1040 1030 1020 1010 1000 990 980
[Hz]
Figure 216 : The XY part of ABXY
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Four-Spin Systems
1 31
400 MHz H{ P} NMR Spectrum of Cl(O)C-CH2-CH2-P(CH3)(O)Cl (30% in CDCl3)
XY Part AB Part
988.997 0.629 1323.204 0.427
994.902 0.670 1329.082 0.475
998.313 0.640 1332.433 0.320
1004.234 0.691 1338.379 0.379
1004.279 1.285 1341.897 1.672
1010.091 1.304 1347.710 1.552
1013.687 1.375 1351.162 1.649
1019.535 1.397 1354.340 1.670
1033.840 1.280 1357.067 1.526
1039.876 1.354 1360.431 1.668
1043.197 1.326 1363.783 1.530
1049.122 0.621 1369.783 1.528
1049.197 1.403 1373.083 0.422
1055.249 0.619 1379.160 0.340
1058.387 0.690 1382.441 0.453
Perform the ABXY analysis starting off from frequencies and intensities given in the table above.
Analyze:
a) the AB part with ABMX approximation and determine NMR data for abmx sub-spectra,
b) the XY part with AMXY approximation and determine NMR data for amxy sub-spectra.
Combine the abmx and the amxy sub-spectral data to form the total ABXY system.
During the course of analysis you will meet the problem of conjugate solutions for this 400 MHz
1H{31P} NMR spectrum.
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Four-Spin Systems
Two sets of NMR parameters are found:
Ambiguities in ABXY Spectral Analysis

Parameter Results
Set 1 Set 2
νA 1368.21 1368.21
νB 1343.14 1343.13
νX 1047.92 1047.93
νY 1005.70 1005.70
JAB -18.70 -18.70
JAX 9.87 5.49
JAY 5.39 9.87
JBX 5.47 9.93
JBY 9.89 5.33
JXY -15.30 -15.29
Simulations of AB- and XY parts for set 1 and set 2 are shown below. Spectra for both sets are
congruent.
Simulation of AB Part
3.48 3.44 3.40 3.36 3.32
3.48 3.44 3.40 3.36 3.32

(ppm)
Figure 217 : 400 MHz Simulation of AB part from ABXY. Lower: Set 1. Upper: Set 2.
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Four-Spin Systems
Simulation of XY Part
2.64 2.60 2.56 2.52 2.48
2.64 2.60 2.56 2.52 2.48

(ppm)
Figure 218 : 400 MHz Simulation of XY part from ABXY. Lower: Set 1. Upper: Set 2.
But only set 2 is correct, which can be confirmed by inspecting a more complex spectrum at lower
field, in our case at 90 MHz. Corresponding simulations are shown below as overview spectra.
Remember: While the conjugate solutions from 400 MHz yield congruent spectral simulations, the
corresponding 90 MHz spectra are not congruent. And only coupling constants following set 2 are
true.
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Simulation of ABXY Spectrum
3.6 3.4 3.2 3.0 2.8 2.6 2.4
3.6 3.4 3.2 3.0 2.8 2.6 2.4

(ppm)
Figure 219 : 90 MHz Simulation of the total ABXY spectrum. Lower: Set 1. Upper: Set 2.
Remember: A set of coupling constants is field invariant, independent of B0. Hence experiments at
different fields will lead to field dependent resonance frequencies but to a unique set of coupling
constants.
Full ABXY iteration of set 2 yields the final values:
Parameter Type [Hz]

νA νH 1368.214
νB νH 1343.134
νX νH 1047.925
νY νH 1005.696
2
JAB JHH -18.699
3
JAX JHH 5.493
3
JAY JHH 9.868
3
JBX JHH 9.931
3
JBY JHH 5.332
2
JXY JHH -15.287
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8.5.3 Further Examples: Heteronuclear ABXY Spin Systems
3 5 3 3 3 5
Since JHH >> JHH the combination of coupling constants ( JHH and JFF) or ( JHH and JFF) give rise
to ABXY spectra from fluorinated benzene derivatives
Cl F F
H F H Cl H F
H F H Br H Cl
Br F Cl
5 3 5 5
while ( JHH and JFF) or ( JHH and JFF) lead to AMXY or AMRX spectra.
H H
F Cl Cl F
F Br F Br
H H
More generally the limiting cases of ABXY are summarized by the following graphic:
ABMX
ABCD ABXY AMRX
AMXY
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8.6 The ABCX System – Spin System No. 20
ABCX spectra have been widely investigated at an early stage of NMR when fields and frequencies
were low.
Typical examples investigated are shown below:
Aliphatic Compounds
R1 R2 R1 R2 R1 R2
H C C C(O)H H C C F H C C P*
H H H H H H
1 2 1 2 1 2
CR H2-CR HC(O)H CR H2-C R HF CR H2-CR HP*
Cyclo-aliphatic Compounds
R H R H
C C C C
H H R H H R
C C
F P*
trans-1,2-R2-C3H3F trans-1,2-R2-C3H3P*
Olefinic Compounds
H H H H
C C C C
H C(O)H H C(O)F
CH2=CHC(O)H CH2=CHC(O)F
H H H H
C C C C
H F H P*
CH2=CHF CH2=CHP*
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Aromatic Compounds
R1 R1
H R2 H F
H F H R2
H H
1 2 1 2
1-R -2-R -3-F-C6H3 1-R -2-F-3-R -C6H3
Heterocyclic Compounds
H H
H R H H
H N F R N F
2-F-3-R-C5H3N 2-F-6-R-C5H3N
With the advent of high field spectrometers many of those ABCX problems simplified to ABMX and
AMRX spectra.
But still the intriguing patterns of ABCX will be found in the following practical examples:
CH2=CHC(O)F, CH2=CHP*
with a rigid ABC part like
- 2-
(P* = P(O)Cl2, P(O)(OR)2, PO3H2, PO3H , PO3 )
CH2Br-CHBrP*
with a rotating ABC part like
(P* = P(O)(OR)2)
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8.6.1 Example 1: Vinyl Fluoride and Acryloyl Fluoride
H H 2 3 H H
C C C C
H F 1 4 H C(O)F
Vinyl fluoride exhibits an ABCX pattern at low fields ( ≤ 60 MHz 1

H NMR), but approaches AMRX (
≥ 200 MHz). Acryloyl fluoride shows more second order character. a) up to 300 MHz: ABCX; b)
at 500 MHz: approximating AMNX; c) at 1000 MHz still not reaching AMRX.
CH2=CHF CH2=CHC(O)F
δ1 H1 4.7423 [ppm] H1 6.5990
δ2 H2 4.4188 [ppm] H2 6.2460
δ3 H3 6.6077 [ppm] H3 6.1395
δ4 F4 F4
2 2
J12 JHH -3.21 [Hz] JHH 0.7
3 3
J13 JHH(trans) 12.67 [Hz] JHH(trans) 17.28
3 3
J23 JHH(cis) 4.72 [Hz] JHH(cis) 10.66
3 4
J14 JFH(cis) 20.51 [Hz] JFH(cis) -0.37
3 4
J24 JFH(trans) 53.44 [Hz] JFH(trans) 2.77
2 3
J34 JFH(gem) 85.44 [Hz] JFH 8.97
While vinyl fluoride has a fixed molecular geometry acryloyl fluoride appears in two different
rotameric forms, hence the choice of solvents and temperature affects the NMR parameters of
acryloyl fluoride.
H H H H
C C C C
H C O H C F
F O
The following spectral data were derived from 50 % acryloyl fluoride in CFCl3 at 18°C.
A maximum of 30 lines is expected for the ABC part of an ABCX system.
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1350 1320 1290 1260 1230

(Hz)
1
Figure 220 : 200 MHz H NMR spectrum of acryloyl fluoride. ABC part of ABCX.
The ABC part of an ABCX can be broken down into two sets of abc sub-spectra for mX = +1/2 and
mX = -1/2.
1350 1320 1290 1260 1230

(Hz)
Figure 221 : abc sub-spectrum for mX = +1/2 (alpha)
1350 1320 1290 1260 1230

(Hz)
Figure 222 : abc sub-spectrum for mX = -1/2 (beta)
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Both abc sub-spectra show some amn character which can be approximated as axy thus allowing
to extract starting data for the effective Larmor frequencies:
1 1
[1] ν a1 =ν A + JAX [4] νa2 =ν A − JAX
2 2
1 1
[2] νb1 =νB + JBX [5] νb2 =νB − JBX
2 2
1 1
[3] ν c1 =ν C + JCX [6] ν c2 =ν C − JCX
2 2
The retro-combination of those effective Larmor frequencies will lead to resonance frequencies νA,
νB, νC and coupling constants JAB, JAC, JBC, JAX, JBX, JCX. There is only one combination which
1 19
satisfies the fluorine-decoupled H{ F} NMR spectrum leaving the parent ABC with identical
resonance frequencies νA, νB, νC and coupling constants JAB, JAC, JBC.
1350 1320 1290 1260 1230

(Hz)
1 19
Figure 223 : Fluorine-decoupled H{ F} NMR spectrum. ABC spectrum.
Compare the characteristic pattern with both abc sub-spectra shown above.
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19
The final proof for analysis is the F NMR spectrum:
N = JAX+JBX+JCX
15 10 5 0 -5 -10 -15
(Hz)
19
Figure 224 : 188 MHz F NMR spectrum (X part) of acryloyl fluoride, centered at 0 Hz.
This X part of an ABCX system consists of eight strong and two weak lines. The difference ν3 - ν8
corresponds to N = JAX + JBX + JCX.
Simulation of the X Part Arbitrarily Centered at νx = 0 Hz.
Line Frequency Intensity Assign

[Hz] [rel]
1 17.4585 0.0116
2 5.9648 0.9999
3 5.6850 1.0000 N-line
4 3.0430 0.9990
5 2.2678 0.9883
6 -2.5476 0.9883
7 -2.7473 0.9990
8 -5.6850 1.0000 N-line
9 -5.9808 0.9999
10 -17.7383 0.0116
Iterate the final data set as ABCX case.
Remarks: This ABCX study is based upon data modified from “Nuclear Magnetic Resonance
Studies of the Rotational Equilibrium in Acryloyl Fluoride” by D. F. Koster. J. Amer. Chem. Soc. 88,
5067-5071 (1966).
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8.6.2 Example 2: ABCX in CH2=CH-P(O)Cl2
Vinyl phosphonic acid dichloride is a suitable model to study a heteronuclear ABCX system.
H H 2 3
C C
H P(O)Cl2 1 4
1
H NMR Spectra of CH2=CH-P(O)Cl2 50% in C6H6
420 400 380 360 340 320

(Hz)
1
Figure 225 : 60 MHz H NMR spectrum of CH2=CH-P(O)Cl2 50% in C6H6.
1320 1280 1240 1200

(Hz)
1
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3240 3200 3160 3120 3080 3040 3000

(Hz)
1
Sub-spectral analysis of the 500 MHz spectrum is simple. Red: 8 lines from A.
Blue: 8 lines from B. Green: 8 Lines from C. Approximate ABCX as AMRX system. Find absolute
values of coupling constants as repeated spacings. Iterate as ABCX.
Remarks
The spectral pattern of CH2=CH-P(O)Cl2 depends on solvent effects. Dimethylsulphoxide is a strong

polar solvent and stabilizes solutes as conformers with high dipole moments.
But do NOT dissolve acyl chlorides or phosphonyl chlorides in dimethylsulphoxide!
Poisonous methyl-chloromethyl-mercaptane CH3-S-CH2Cl is formed:
RP(O)Cl2 + 2 (CH3)2SO  RP(O)(OH)2 + 2 CH3-S-CH2Cl
1 1
Since the 60 MHz H NMR spectrum is too complex and the 500 MHz H NMR spectrum too simple,
it is useful to look deeper into the 200 MHz spectra of CH2=CH-P(O)Cl2.
A maximum of 30 lines is expected for the ABC part of an ABCX system.
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1320 1280 1240 1200 1160

(Hz)
1
Figure 228 : 200 MHz H NMR spectrum of CH2=CH-P(O)Cl2. ABC part.
1
The 200 MHz H NMR spectrum appears fairly complex but with experience acquired in the chapter
on ABC (7.5) it is not too difficult to separate the total ABCX into the two abc sub-spectra generated
31
from spin states of the X-nucleus ( P) with mX=+1/2 and mX=-1/2.
1320 1280 1240 1200 1160

(Hz)
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1320 1280 1240 1200 1160

(Hz)
Both abc sub-spectra show some abx character thus allowing to extract starting data for the
effective Larmor frequencies following equations [1] to [6] listed above.
The retro combination of those effective Larmor frequencies leads to resonance frequencies νA, νB,
νC and coupling constants JAB, JAC, JBC, JAX, JBX, JCX.

1 31
There is only one combination which satisfies the phosphorous-decoupled H{ P} NMR spectrum
leaving the parent ABC with identical resonance frequencies νA, νB, νC and coupling constants JAB,
JAC, JBC.
1320 1280 1240 1200 1160

(Hz)
1 31
Figure 231 : H{ P} NMR spectrum. ABC spectrum.
Compare the characteristic pattern with both abc sub-spectra shown above. In addition study the
31
proton coupled P NMR spectrum, which corresponds to the X part of this ABCX system.
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Only 8 strong lines - practically of equal intensity - are observed:
1 23 45 67 8
80 40 0 -40 -80
(Hz)
31
Figure 232 : 81 MHz P NMR spectrum. X part.
which exhibit a deceptively simple pattern. At first sight it is tempting to extract 3 repeated
spacings for JAX, JBX and JCX resp.. But there is no repeated spacing!
Differences Between Pairs of Lines

Lines Difference Lines Difference Lines Difference Lines Difference
[Hz] [Hz] [Hz] [Hz]
1,2 35.8952 3,4 31.0528 5,6 31.1207 7,8 36.2083
1,3 40.6260 2,4 35.7836 5,7 35.3479 6,8 40.4355
1,5 76.6438 2,6 71.8693 3,7 71.3657 4,8 76.5212
A crude guess leads to three averaged separations 35.8 Hz, 40.5 Hz, and 71.6 Hz which come
close to J24 = 35.55 Hz, J34 = 40.78 Hz, and J14 = 71.87 Hz.
Only one distance is analytically relevant and correct. N, the sum of coupling constants, is
derived from strong lines ν1 and ν8:
[7] ν1 −ν=8 JAX + JBX + JCX

= N
N is found to be 148.2 Hz which indeed corresponds to the sum of coupling constants as defined
above. Obviously the N-lines ν1 and ν8 belong to those spin states of A, B and C where mA and mB
and mC simultaneously are either +1/2 or -1/2.
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The resonance frequency νX is identical with the mean of all 8 lines ν1 to ν8. But only one pair of
lines is symmetrically placed around νX
1
[8] ν X= (ν1 + ν 8 )
2
Addendum
8 very weak combination lines are expected, 6 of which are visible in the intensity-expanded
spectrum of the X part:
80 40 0 -40 -80
(Hz)
31
Figure 233 : 81 MHz PNMR spectrum. X part. Intensity-expanded.
Those combination lines are not used to analyze the spectrum of CH2=CH-P(O)Cl2.
Applying the starting data obtained above in a final ABCX iteration of the proton NMR spectrum
leads to:
Results for CH2=CH-P(O)Cl2, 50% in C6H6, at 200 MHz
Parameter Data [Hz]

ν1 νH1 1258.8614
ν2 νH2 1213.8013
ν3 νH3 1286.7614
ν4 νP4
)
0.00 *
2
J12 JHH(gem) 0.26
3
J13 J23(trans) 18.08
3
J23 JHH(cis) 11.94
2
J14 JPH(cis) 35.55
3
J24 JPH(trans) 71.87
2
J34 JPH(gem) 40.78
HWB global 0.30
*) by definition.
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8.6.3 Example 3: ABCX in CH2=CH-P(O)(OiPr)2 and CH2Br-CHBr-P(O)(OiPr)2
Vinyl phosphonic acid di-iso-propylester 1 reacts with elemental bromine to form 1,2-di-bromo-
1
ethane-phosphonic acid di-iso-propylester 2. H NMR spectra characterize the olefinic and aliphatic
protons in both compounds as ABC parts of ABCX systems.
H H 2 3 H H 2 3
C C P* = P(O)(OiPr)2 H C C P* 1 4
H P* 1 4 Br Br
1 2
The vinylic skeleton of vinyl phosphonic acid di-iso-propylester 1 exhibits an ABCX pattern even at
1
higher fields (500 MHz H NMR).
The ethane skeleton of 1,2-dibromo-ethanephosphonic acid di-iso-propylester 2 shows less second
order character, an ABCX up to 200 MHz, but at 500 MHz a neat AMRX.
CH2=CH-P* 1 CH2Br-CHBrP* 2
δ1 H1 6.246 [ppm] H1 3.996
δ2 H2 6.070 [ppm] H2 4.096
δ3 H3 6.068 [ppm] H3 3.600
δ4 P4 0 by def. [ppm] P4 0 by def.

2 2
J12 JHH 2.145 [Hz] JHH 3.39
3 3
J13 JHH(trans) 18.77 [Hz] JHH 10.59
3 3
J23 JHH(cis) 12.73 [Hz] JPH -11.88
3 3
J14 JPH(cis) 25.08 [Hz] JPH -11.53
3 2
J24 JPH(trans) 50.84 [Hz] JPH 6.46
2 3
J34 JPH(gem) 21.54 [Hz] JHH 6.42
While the vinyl phosphonic skeleton may be regarded as fixed the 1,2-dibromoethane phosphonic
unit can be described by 3 canonical rotamers, hence the choice of solvents and temperature
affects the NMR parameters of compound 2 considerably.
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H1 H1 H1
Br H2 H3 Br H2 H3
C C C
Br P* Br P* Br P*
H3 H2 Br
I II III
It can be shown, that rotamer I is dominant in this rotameric equilibrium.
Compound 1 - CH2=CH-P(O)(OiPr)2
The following spectra and data were derived from a 30% solution of CH2=CH-P(O)(OiPr)2 in CDCl3
at ambient temperature.
1
Simulated 200 MHz H NMR Spectrum of CH2=CH-P(O)(OiPr)2
1280 1260 1240 1220 1200 1180

(Hz)
1
Figure 234 : 200 MHz H NMR spectrum of CH2=CH-P(O)(OiPr)2. ABC part.
1280 1260 1240 1220 1200 1180

(Hz)
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1280 1260 1240 1220 1200 1180

(Hz)
Both abc sub-spectra are difficult to analyze manually. The moment method can be used to
evaluate the effective Larmor frequencies νai, νbi, and νci (i=1,2), see also chapter 7.5.8.The retro-
combination of those effective Larmor frequencies will lead to resonance frequencies νA, νB, νC and
coupling constants JAX, JBX, JCX. There is only one combination which satisfies the phosphorous-
decoupled H{ P} NMR spectrum leaving the parent ABC with identical resonance frequencies νA,
1 31
νB, νC and coupling constants JAX, JBX, JCX.
1280 1260 1240 1220 1200 1180

(Hz)
1 31
Figure 237 : H{ P} NMR spectrum of CH2=CH-P(O)(OiPr)2. ABC spectrum.
Manual analysis is difficult. Resonance frequencies νA, νB, νC are accessible from this
phosphorous-decoupled proton NMR spectrum via the moment method.
Compare the characteristic pattern with both abc sub-spectra shown above. Iterate the final data set
as ABCX case.
3
The proton coupled phosphorus NMR spectrum is not useful for CH2=CH-P(O)(OiPr)2. JPOCH and
4 31
JPOCCH couplings add to the splitting induced by the CH2=CH unit. P NMR reflects a total system
of ABC[MR3T3]2X system (M = OCH; R, T = CCH3).
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Compound 2 - CH2Br-CHBr-P(O)(OiPr)2
The following spectra and data were derived from a 30% solution of CH2Br-CHBr-P(O)(OiPr)2 in
CDCl3 at ambient temperature.
820 800 780 760 740 720 700

(Hz)
1
Figure 238 : 200 MHz H NMR spectrum of CH2Br-CHBr-P(O)(OiPr)2. ABC part.
820 800 780 760 740 720 700

(Hz)
820 800 780 760 740 720 700

(Hz)
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Both abc sub-spectra show some abx character thus allowing to extract starting data for the
effective Larmor frequencies νai, νbi, and νci (I = 1,2) and coupling constants JAX, JBX and JCX.
Remember the unusual pattern of the abc sub-spectrum for mX = -1/2 (beta) shown in the
figure above.
The retro-combination of those effective Larmor frequencies will lead to resonance frequencies νA,
νB, νC and coupling constants JAB, JAC, JBC, JAX, JBX, JCX. There is only one combination which
1 31
satisfies the phosphorous-decoupled H{ P} NMR spectrum leaving the parent ABC with identical
resonance frequencies νA, νB, νC and coupling constants JAB, JAC, JBC.
4.10 4.00 3.90 3.80 3.70 3.60 3.50

(ppm)
1 31
Figure 241 : H{ P} NMR spectrum of CH2Br-CHBr-P(O)(OiPr)2. ABC spectrum.
Resonance frequencies νA, νB, νC and coupling constants JAB, JAC, and JBC are easily accessible (as
an ABX approximation) from this phosphorous-decoupled proton NMR spectrum.
Compare the characteristic pattern with both abc sub-spectra shown above. Iterate the final data set
as ABCX case.
3 3
Vicinal coupling constants JHH and JPH depend on dihedral angles ∝ (H-C-C-H) and
∝ (P-C-C-H) resp. and follow modified KARPLUS type functions.
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The following data
H2 4.096 ppm H2 trans to Br

H3 3.600 ppm H3 trans to H1
3
JHH(1,2) 3.39 Hz gauche
3
JHH(1,3) 10.59 Hz trans
3
JPH(2,4) 6.46 Hz gauche
3
JPH(3,4) 6.42 Hz gauche
are consistent with dominant rotamer I
Remarks
This ABCX study is based upon modified data given in

1
“Applications of Spectral Moments. Analysis of H NMR Spectra of Vinyl Phosphonic Acid
Derivatives”. H. Dolhaine, M. Engelhardt, G. Hägele, W. Kückelhaus. J. Magn. Res. 41,1-16 (1980).
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8.6.4 Example 4: pH-Dependent ABCX Spectra
Vinyl phosphonic acid CH2=CH-PO3H2 (H2L) is a two-basic acid forming by deprotonation the two
- - 2- 2-
anions CH2=CH-PO3H (HL ) and CH2=CH-PO3 (L ). Specific NMR parameters are affiliated with
1 31
those three protolytic species giving rise to individual H and P NMR spectra as shown below:
1 i-2
Specific H NMR Parameters for CH2=CH-P(O)(OH)2 and Anions HiL (i = 2 to 0)
Protolytic Species
- 2-
Parameters H2L HL L
δ1 ppm 6.2796 5.8863 5.6930
δ2 ppm 6.2463 5.7931 5.5525
δ3 ppm 6.2520 6.1488 6.1346
δ4 ppm
ν1 Hz 3140.59 2943.91 2847.26
ν2 Hz 3123.97 2897.32 2776.97
ν3 Hz 3126.83 3075.19 3068.08
ν4 Hz
J12 Hz 1.371 2.337 3.001
J13 Hz 18.809 18.857 18.892
J23 Hz 13.015 12.842 12.776
J14 Hz 26.763 23.224 21.109
J24 Hz 53.087 46.152 42.036
J34 Hz 24.96 20.259 17.570
The fully protonated species CH2=CH-P(O)(OH)2 (H2L) gives rise to a strongly coupled ABCX
system. Deprotonation affects remarkably the proton resonance frequencies and the phosphorous-
proton coupling constants as well. Note the change from ABCX to AMRX spectrum for CH2=CH-
- - 2- 2-
PO3H (HL ) and CH2=CH-PO3 (L ).
See corresponding spectra below:
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Four-Spin Systems
1 i-2
500 MHz H NMR Spectra of CH2=CH-P(O)(OH)2 and Anions HiL (I = 2 to 0)
3100 3000 2900 2800

(Hz)
1
Figure 242 : 500 MHz H NMR spectrum of CH2=CH-PO3H2 H2L
3100 3000 2900 2800

(Hz)
1 - -
Figure 243 : 500 MHz H NMR spectrum of CH2=CH-PO3H HL
3100 3000 2900 2800

(Hz)
1 2- 2-
Figure 244 : 500 MHz H NMR spectrum of CH2=CH-PO3 L
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The assignment of shifts and coupling constants is confirmed by the following 500 MHz HH-COSY
spectrum:
(ppm)
5.60
5.80
6.00
6.20
(ppm) 6.20 6.00 5.80 5.60 5.40
Figure 245 : 500 MHz H,H-COSY spectrum for CH2=CH-PO3 . Total concentration CT = 0.2 m. τ = 3;
2-
Lock. Solvent: D2O; Ref.: int. TMS-sulfonate.
- 2-
Obviously deprotonation changes the substituent effects of -PO3H2, -PO3H , and -PO3 . This is
affiliated with a down field shift for proton resonances and for phosphorus resonances (obtained by
31 1
P{ H} NMR) as well.
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18 17 16 15 14 13 12
Figure 246 : NMR controlled titration: x-axis: chemical shift δP. Y-axis: degree of titration τ. δ,τ-plot for vinyl
phosphonic acid. Total concentration CT = 0.2 m of vinyl phosphonic acid. From lower to upper trace:
τ-values: -3.0, 0.0, 0.5, 1.0, 1.5, 2.0 und 3.0. The τ-scale is defined by: τ- -3.0 corresponds to a molar
ratio DClO4 / CH2=CH-PO3H2 of 3. τ- +3.0 corresponds to a molar ratio KOD / CH2=CH-PO3H2 of 3.
This downfield effect is also visible in the chemical shift for the β-carbon in CH2=CH-P skeleton
while the α-carbon shows the opposite.
13 1
125.758 MHz C{ H} NMR. Vinyl Phosphonic Acid. CT = 0.2 m.
Species CH2= =CH-P

δC δC
2 1
JPC JPC
CH2=CH-PO3H2 134.6205 0 127.0022 177.72
-
CH2=CH-PO3H 128.8740 0 132.7211 171.36
2-
CH2=CH-PO3 124.7525 0 137.1833 165.01
Hence define precisely the state of solution when characterizing acids (or bases).
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8.7 The ABX2 System – Spin System No. 23
8.7.1 Practical Example 1: The 1H NMR Spectrum of Trans-CHCl=CH-CH2Cl
1
The 500 MHz H NMR spectrum of trans-CHCl=CH-CH2Cl is due to a homonuclear ABX2 system:
H2 HB
Cl C Cl Cl C Cl
C C C C
H1 H3 H3 HA HX HX
1
H NMR Data
Parameter Type Data

δ1 δH 6.315 ppm
δ2 δH 6.053 ppm
δ3 δH 4.010 ppm
ν1 νH 3157.5 Hz
ν2 νH 3026.5 Hz
ν3 νH 2005.0 Hz
3
J12 JHH 13.1 Hz
4
J13 JHH -1.1 Hz
3
J23 JHH 7.2 Hz
1
H NMR data for trans-CHCl=CH-CH2Cl. Calculated for 500 MHz.
δH and νH vs. int. TMS. Solvent: CCl4.
1
While a 60 MHz H NMR spectrum of trans-CHCl=CH-CH2Cl reveals ABC2 character AMX2 is
observed at 500 MHz. An intermediate situation is met at 200 MHz: an ABC2 case with proximity to
1
ABX2. Here we will study the analysis of ABX2 spectra. The 500 MHz H NMR spectrum of trans-
CHCl=CH-CH2Cl reveals well separated A-, B-, and X2-regions.
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The total spectrum and corresponding expansion for A, B, and X2 parts are shown below:
6.0 5.6 5.2 4.8 4.4 4.0

(ppm)
1
Figure 247 : 500 MHz H NMR spectrum. Calculated as ABC2.
6.0 5.6 5.2 4.8 4.4 4.0

(ppm)
1
Figure 248 : 500 MHz H NMR spectrum. Calculated as ABX2.
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The A and the B parts appear as triplets of ab sub-spectra:
3172 3168 3164 3160 3156 3152 3148 3144

(Hz)
1
Figure 249 : 500 MHz H NMR spectrum. Calculated as ABC2. A part.
3172 3168 3164 3160 3156 3152 3148 3144

(Hz)
1
Figure 250 : 500 MHz H NMR spectrum. Calculated as ABX2. A part.
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3040 3036 3032 3028 3024 3020 3016 3012

(Hz)
1
Figure 251 : 500 MHz H NMR spectrum. Calculated as ABC2. B part.
3040 3036 3032 3028 3024 3020 3016 3012

(Hz)
1
Figure 252 : 500 MHz H NMR spectrum. Calculated as ABX2. B part.
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Effective Larmor frequencies for those ab sub-spectra are given by:
[1] νa =ν A + mT (X2 ) ⋅ JAX [5] νb =νB + mT (X2 ) ⋅ JBX mT (X2 )

[2] νa1 =ν A + JAX [6] νb1 =νB + JBX +1
[3] νa2 =
νA [7] νb2 =
νB 0
[4] νa3 =ν A − JAX [8] νb3 =νB − JBX -1
Numerical results for those effective Larmor frequencies are listed below:
Sub-spectrum mT(X2) νai νbi

i [Hz] [Hz]
1 +1 3156.95 3022.90
2 0 3157.50 3026.50
3 -1 3158.05 3030.10
Obviously it suffices to analyze the central ab sub-spectrum (i = 2; mT(X2) = 0)) in order to obtain νA,
νB and JAB.
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The averaged triplet splittings correspond to the absolute values of coupling constants JAX and JBX
resp. Calculated transition frequencies and intensities are listed below:
ABC2 ABX2
A Part
1 3165.4571 0.9040 3165.4573 0.9064
2 3164.3774 0.9005
3164.3767 1.8010
3 3164.3767 0.9005
4 3163.2996 0.8962 3163.2987 0.8938
5 3152.3576 1.0922 3152.3573 1.0936
6 3151.2783 1.0995
3151.2767 2.1990
7 3151.2767 1.0995
8 3150.2001 1.1075 3150.1987 1.1062
B Part
9 3039.9260 1.0917 3039.9013 1.1062
10 3032.7735 1.0994
3032.7233 2.1990
11 3032.7233 1.0995
12 3026.8264 0.8803 3026.8013 0.8938
13 3025.5682 1.1082 3025.5427 1.0936
14 3019.6744 0.9003
3019.6233 1.8010
15 3019.6233 0.9005
16 3012.4687 0.9201 3012.4427 0.9064
C Part X Part
17 2009.1295 2.0160 2009.1306 2.0000
18 2009.1022 2.0159 2009.1280 2.0000
19 2008.0498 2.0122
2008.0500 4.0000
20 2008.0244 2.0121
21 2001.9502 1.9879
2001.9500 4.0000
22 2001.9238 1.9877
23 2000.8719 1.9842 2000.8720 2.0000
24 2000.8445 1.9840 2000.8694 2.0000
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The center frequency of the X2 part corresponds to νX. An approximation holds: Absolute values are
found for linear combinations N = JAX + JBX and L = JAX-JBX.
1
Figure 253 : 500 MHz H NMR spectrum. Calculated as ABC2. C part.
2016 2012 2008 2004 2000 1996 1992

(Hz)
1
Figure 254 : 500 MHz H NMR spectrum. Calculated as ABX2. X part.
1
Minute differences between calculated ABC2 and ABX2 spectra show, that the 500 MHz H NMR
spectrum of trans-CHCl=CH-CH2Cl is dominantly ABX2. Thus the ABX2 sub-spectral approach to
trans-CHCl=CH-CH2Cl is fully justified.
For details of a 60 MHz study see: E. W. Garbisch Jr.; J. Chem. Ed. 45, 480-493 (1968)
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8.7.2 Practical Example 2: ABX2 in Cis-1,2-Dichlorotetrafluorocyclopropane
19 13
Cavalli described F and C NMR studies of 1,2-dichlorotetrafluorocyclopropanes and
characterized the ABX2 spectrum of:
Corresponding NMR data are listed below:
Parameter Data
δ1 δF -153.1 ppm
δ2 δF -139.9 ppm
δ3 δF -165.5 ppm
2
J12 JFF (gem) +173.1 Hz
3
J13 JFF (cis) +5.62 Hz
3
J23´ JFF (trans) -5.25 Hz
19
F NMR data for ABX2 system in cis-1,2-dichlorotetrafluorocyclopropane
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19
A simulated 94 MHz F NMR spectrum and corresponding expansions for the ABX2 system in cis-
1,2-dichlorotetrafluorocyclopropane are shown below:
-140 -144 -148 -152 -156 -160 -164

(ppm)
Figure 255 : Total ABX2 spectrum
Expanded spectra of A-, B- and X2-regions are shown below:
-13040 -13080 -13120 -13160 -13200 -13240

(Hz)
Figure 256 : A part from ABX2 system.
-14320 -14360 -14400 -14440 -14480 -14520

(Hz)
Figure 257 : B part from ABX2 system.
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-15480 -15520 -15560 -15600 -15640 -15680

(Hz)
Figure 258 : X part from ABX2 system.
Figure 259 : Expanded X part from ABX2 system.
This is another interesting case where |N| < |L|.
3 3
N JAX + JAX´ JFF (cis) + JFF (trans) 0.37 Hz
3 3
L JAX - JAX´ JFF (cis) - JFF (trans) 10.87 Hz
3 3 19
Hence signs of JFF (cis) and JFF (trans) must be opposite. Relative signs were determined by F
13 13
and C NMR of C-isotopomers from cis-1,2-dichlorotetrafluorocyclopropane and related
compounds. For details read: L. Cavalli; Org. Magn. Res. 2, 233-244 (1970).
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Appendix: Transition Frequencies and Intensities for ABX2 Spectra
Explicit equations for transition frequencies and intensities were derived and listed below. The
following auxiliary parameters will be used:
1 [11] =
N JAX + JBX
[9] z= ( ν A + νB )
2
[10] ∆ = ν A − νB [12] =
L JAX − JBX
1 1
[13] =
C1 ( ∆ − L)2 + J2AB [16] D=1 ( ∆ − L)
2 2
1 1
[14] C=
2 ∆ 2 + J2AB [17] D2= ∆
2 2
1 1
=
[15] C 3 ( ∆ + L)2 + J2AB [18] D3= ( ∆ + L)
2 2
1 1
D1 ⋅ D2 + J2AB D2 ⋅ D3 + J2AB
[19] E = 4 [20] F = 4
C1 ⋅ C2 C 2 ⋅ C3
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12 lines are Calculated for the AB Part, Divided into 4 Lines Each for 3 ab Sub-spectra
ab Sub-spectrum 1
1 JAB
1 z − C1 − JAB + N 1−
2 2C1
1 JAB
2 z − C1 + JAB + N 1+
2 2C1
1 JAB
3 z + C1 − JAB + N 1+
2 2C1
1 JAB
4 z + C1 + JAB + N 1−
2 2C1
ab Sub-spectrum 2
1 JAB
1 z − C2 − JAB 2−
2 2C2
1 JAB
2 z − C2 + JAB 2+
2 2C2
1 JAB
3 z + C2 − JAB 2+
2 2C2
1 JAB
4 z + C2 + JAB 2−
2 2C2
ab Sub-spectrum 3
1 JAB
1 z − C3 − JAB − N 1−
2 2C3
1 J
2 z − C3 + JAB − N 1+ AB
2 2C3
1 J
3 z + C3 − JAB − N 1+ AB
2 2C3
1 J
4 z + C3 + JAB − N 1− AB
2 2C3
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6 Lines are Calculated for the X2 Part

X2 Part
1− E
1
ν X − C1 − C2
1
2 νX − N 4
2
1+ F
3
ν X + C 2 − C3
1+ F
4
ν X − C 2 + C3
1
5 νX + N 4
2
1− E
6
ν X + C1 + C2
Followed by 4 Combination Lines

Combination lines
1− F
1
ν X − C 2 − C3
1+ E
2
ν X + C1 − C2
1+ E
3
ν X − C1 + C2
1− F
4
ν X + C 2 + C3
Hence a maximum of 22 lines are calculated for the total ABX2 spectrum.
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Remarks: The following weak lines from the X2 part might not be observed and in addition will be
suppressed by calculations using LAOCOON and DAISY type programs:
1− E
1
ν X − C1 − C2
1− E
6
ν X + C1 + C2
1− F
1
ν X − C 2 − C3
1− F
4
ν X + C 2 + C3
Hence in practice we expect a total of 18 lines for the ABX2 spectrum.
Exercise: Discuss the spectral appearance of 3 isomeric dichloropropenes:
H Cl Cl H H H
C C C C C C
H CH2Cl H CH2Cl Cl CH2Cl
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8.8 The A2BX and the AB2X System – Spin System No. 24
In this section we will study two examples: the true AB2X spectra from allene-substituted
phosphorus compounds (CH2=C=CHPR2, CH2=C=CHP(O)R2) and the analogous A2BX system of
the aromatic compound C6H3FCl2. For practical reasons we will start with the A2BX case.
8.8.1 Practical Example 1: The A2BX Spectrum of 1-Fluoro-2,6-dichlorobenzene
By some chemical transformations we obtained a hitherto unknown isomer of dichloro-fluoro-

benzene C6H3Cl2F. Six possible structures and expected spin systems are shown below:
F F F
H Cl H Cl H Cl
H Cl H H Cl H
H Cl H
ABCX ABCX ... ABMX ABCX ... ABMX
F F F
Cl Cl H H H H
H H H Cl Cl Cl
H Cl H
A2BX ABCX ... ABMX A2BX ... A2MX
Figure 260 : Isomeric Structures of C6H3Cl2F
19 1
The proton decoupled F{ H} NMR spectrum appears as a singlet. This would be true for all 6
1 19
isomers. The fluorine decoupled H{ F} NMR proton spectrum shows A2B features resembling the
spectrum of 1,2,3-trichlorobenzene discussed above in chapter 7.7. This observation excludes 4
from the total of 6 isomers.
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25 15 5 -5 -15 -25
(Hz)
1 19
Figure 261 : H{ F} NMR: A2B.
Since JHH(ortho) > JHH(meta) the observed JAB points towards 1-fluoro-2,6-dichlorobenzene
excluding 1-fluoro-3,5-dichlorobenzene with its (small) JHH(meta) coupling constants.
1 19
H{ F} Decoupled A2B Spectrum
Parameter [Hz]
ν1 νA2 6.8760
ν2 νB -6.8760
J12 JAB 8.1800
HWB global 0.3000
Line number Frequency Intensity

1 25.0443 0.0083
2 13.6712 0.7351
3 9.9718 1.3028
4 4.4970 2.6889
5 3.7802 3.2566
6 -1.4012 2.2649
7 -6.8760 1.0000
8 -11.2923 0.4323
9 -16.7670 0.3111
1 19
H and F NMR studies of 1-fluoro-2,6-dichloro-benzene reveal the characteristic pattern of an
A2BX system.
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0.25 0.15 0.05 -0.05 -0.15 -0.25

(ppm)
1
Figure 262 : H NMR: A2B part of A2BX
-980 -990 -1000 -1010 -1020

(Hz)
19
Figure 263 : F NMR: X part of A2BX. See four weak lines.
Modified NMR parameters used for plots: ∆ν = (νA – νB)= 13.752 Hz. Arbitrary definitions:
Frequencies νA and νB are centered around zero. Frequency νX is set to -1000 Hz.
NMR Parameters for 1-Fluoro-2,6-dichloro-benzene
Parameter [Hz]
ν1 νA 6.876
ν2 νB -6.876
ν3 νX -1000
J12 JAB 8.18
J13 JAX 6.49
J23 JBX -1.65
HWB global 0.30
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Calculated transition frequencies and intensities for A2B- and X parts are listed in two subsequent
tables.
1
H Spectrum: A2B Part of A2BX System

1 31.4878 0.0047
2 19.0484 0.0130
3 16.3226 0.9712
4 13.5325 1.3928
5 11.3495 0.4443
6 7.4641 2.6024
7 6.7095 3.0240
8 6.1995 1.1945
9 1.6480 2.7925
10 1.0625 3.5426
11 -1.4995 2.5557
12 -1.6326 2.0288
13 -6.0510 1.0000
14 -7.7010 1.0000
15 -11.2458 0.5784
16 -11.7864 0.2499
17 -16.3380 0.2075
18 -17.3141 0.3976
19
F Spectrum: X Part of A2BX System

1 -981.3529 0.0435
2 -981.8629 0.0113
3 -994.2018 0.9565
4 -994.3350 1.0000
5 -999.1750 1.0000
6 -999.3082 0.9565
7 -999.8488 0.9887
8 -1000.8250 1.0000
9 -1005.6650 1.0000
10 -1006.6412 0.9887
11 -1012.1571 0.0435
12 -1024.6271 0.0113
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Break Down of A2B Part from A2BX Spectrum into 2 a2b Sub-spectra
The total A2B part from A2BX holds two individual a2b sub-spectra, each representing the 8-line
pattern known from corresponding A2B analysis: Please bear in mind the specific situation of 1-
4 5
fluoro-2,6-dichlorobenzene: sign (JAX = JFH) = positive, sign (JBX = JFH) = negative.
A2 B
νA νB
JAX JBX
νa1 νa2 νb2 νb1
a2b - 1
a2b - 2
sub spectra
Figure 264 : a2b sub-systems from A2BX system.
Effective Larmor Frequencies for a2b Sub-spectra:
1 1 1 1
[1] ν a1 =ν Α + JAX [2] νb1 =νB + JBX [3] ν a2 =ν Α − JAX [4] νb2 =νB − JBX
2 2 2 2
Sub-spectrum 1 Sub-spectrum 2
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The individual a2b sub-spectra 1 and 2 are shown below:
25 15 5 -5 -15 -25
(Hz)
1
Figure 265 : H NMR: a2b sub-spectrum 1
25 15 5 -5 -15 -25
(Hz)
1
Figure 266 : H NMR: a2b sub-spectrum 2
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1
H a2b Sub-spectrum 1
ν1 νA2 11.120
ν2 νB -7.701
J12 JAB 8.18
HWB global 0.3

1 31.4859 0.0047
2 16.3218 0.9712
3 13.5314 1.3928
4 7.4632 2.6024
5 6.7086 3.0241
6 -1.6328 2.0288
7 -7.7010 1.0000
8 -11.2459 0.5784
9 -17.3142 0.3976
1
H a2b Sub-spectrum 2
ν1 νA2 3.630
ν2 νB -6.501
J12 JAB 8.18
HWB global 0.3

1 19.0468 0.0130
2 11.3488 0.4443
3 6.1983 1.1945
4 1.6471 2.7925
5 1.0617 3.5427
6 -1.4998 2.5557
7 -6.0510 1.0000
8 -11.7868 0.2498
9 -16.3381 0.2075
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8.8.2 Practical Example 2: AB2X Spectra from Organo Phosphorus

Chemistry
NMR spectroscopic characterization of allene-substituted phosphines and phosphine oxides lead to

examples of AB2X systems:
H H H H
C C C C C C R = N(CH3)2
H PR2 H P(O)R2
5.4 5.2 5.0 4.8 4.6
5.4 5.2 5.0 4.8 4.6

(ppm)
Figure 267 : AB2 parts from AB2X spectra. Two examples: Upper: CH2C=C=CHPR2. Lower:
CH2C=C=CHP(O)R2. R = N(CH3)2.
Parameters CH2=C=CHPR2 CH2=C=CHP(O)R2

δA δH(A) ppm 5.155 5.425
δB δH(B2) ppm 4.590 4.956

4
JAB JHH Hz 6.90 6.92
2
JAX JPH Hz 17.75 1.44
4
JBX JPH Hz 5.0 -11.92
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Remember: There is a significant dependence of PH-coupling constants on the oxidation state of

phosphorus. Compare the spectral appearance of vinylic and allenic groups in CH2=CHP* and
CH2=C=CHP* derivatives: ABCX and AB2X.
For details read: M.P. Simonin, C. Charrier; Org. Magn. Res. 1, 27-49 (1969).
8.9 The [AX]2 System – Spin System No. 27
JAA´
A A´ 1 2
JAX JAX´
X X´ 3 4
JXX´
For a typical [AX]2 spin system the following symmetry relations must hold:
[1] νA = νA´ ν1 = ν2
[2] νX = νX´ ν3 = ν4
[3] JAX = JA´X´ J13 = J24
[4] JAX´ = JA´X J14 = J23
and
[5] JAX ≠ JAX´
If J = J then the symmetry is higher and the spin system is described by A2X2, a system which
AX AX´
will be discussed in chapter 8.11 of this manuscript.
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The A- and A´-nuclei are chemically equivalent, which is true for nuclei X und X´ as well.
In order to simplify the procedure of spectral analysis it is convenient to introduce linear

combinations of coupling constants as shown below.
[6] N = JAX + JAX´

[7] L = JAX - JAX´
[8] K = JAA´ + JXX´
[9] M = JAA´ - JXX´
The [AX]2 spectrum exhibits a characteristic pattern having a total of 20 transitions divided into two
congruent half spectra, each with 10 lines as 5 pairs, which are arranged symmetrically around νA
and νX resp..
If we want to extract the coupling constants of the [AX]2 system, it is sufficient to inspect one of both
half-spectra. This half spectrum is divided into three components:
1. Two strong lines, called the N-lines, are centered around νA, each contributing 25% of
the total intensity of this half spectrum.
[10] νN1 - νN2 = N
[11] (νN1 + νN2)/2 = νA (or νX resp.)
2. Four lines form the "K"-ab sub-spectrum involving the effective parameters:
[12] ∆νab = L
[13] Jab = K
are centered around νA (or νX resp.).
3. Four lines form the "M"-ab sub-spectrum involving the effective parameters:
[14] ∆νab = L
[15] Jab = M
which again are centered around νA (or νX resp.).
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Each of the "K"- und the "M"-ab sub-spectra contributes 25% to the total intensity of this half
spectrum.
Note: Signs of N, L, K und M do not influence the outer appearance of an [AX]2 spectrum.
If |K| > |M|, then the "K"-ab sub-spectrum forms the outer ab sub-spectrum while the inner ab sub-
spectrum holds the "M"-ab sub-spectrum.
If |K| < |M|, then the "M"-ab sub-spectrum forms the outer ab sub-spectrum while the inner ab sub-
spectrum holds the "K"-ab sub-spectrum.
1 19
Cis-difluoroethylene cis-CHF=CHF gives rise to suitable H and F NMR spectra of [AX]2 type
which will be used to demonstrate the work flow of [AX]2 spectral analysis:
H H A A´
C C
F F X X´
For convenience sake let us center the midpoints frequencies νA or νX to 0 Hz.

The characteristic coupling constants are given by:
Coupling Constants Data [Hz]
JAX = 2 JFH (gem) 71.84
JAX' = 3 JFH (trans) 19.77
JAA' = 3 JHH (cis) -2.07
JXX' = 3 JFF (cis) 19.04
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Linear combinations are calculated to:
Linear Combinations [Hz]

N 91.62
L 52.07
K 16.97
M -21.11
Simulate one of both half-spectra. Straight forward you will obtain:
Simulated Half Spectrum of [AX]2, the A Part or the X Part.
Figure 268 : Simulated half spectrum of [AX]2, the A part or the X part.
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Simulated transition frequencies and intensities are listed below:
Line Frequency Intensity Assignment

No. [Hz] [rel.]
1 45.8050 4.0000 N1
2 38.6482 0.6243 “M“-ab sub-spectrum
3 35.8678 0.6901 “K“-ab sub-spectrum
4 18.8978 1.3099 “K“-ab sub-spectrum
5 17.5382 1.3757 “M“-ab sub-spectrum
6 -17.5382 1.3757 “M“-ab sub-spectrum
7 -18.8978 1.3099 “K“-ab sub-spectrum
8 -35.8678 0.6901 “K“-ab sub-spectrum
9 -38.6482 0.6243 “M“-ab sub-spectrum
10 -45.8050 4.0000 N2
Now try to reanalyze your own simulated spectrum. You will meet a few problems.
While the simulation of an [AX]2 spectrum is simple and unequivocal - when starting off from
known parameters - the analysis of a given spectrum is more complex and more laborious.
Direct analysis of N-lines and ab sub-spectra yields ІNІ and ІLІ, the absolute values for N and L.
In addition two repeated spacings are obtained by direct analysis from the ab sub-spectra, which
can be ІKІ and ІMІ or ІMІ and ІKІ. An unequivocal assignment of “K”- and “M”-ab sub-spectra is
possible by double resonance methods.
Individual coupling constants follow from linear combinations:
|N| + |L| = 2 |JAX| or 2 |JAX´|
|N| - |L| = 2 |JAX´| or 2 |JAX|
|K| + |M| = 2 |JAA´| or 2 |JXX´|
|K| - |M| = 2 |JXX´| or 2 |JAA´|
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Remarks on Signs for Coupling Constants JAX and JAX´:
if |N| > |L| than sign(JAX) = sign(JAX´)
if |N| < |L| than sign(JAX) ≠ sign(JAX´)
Further conclusions regarding the individual signs of coupling constants JAX and JAX´ are not
accessible via direct analysis.

Analogous conclusions hold for JAA´ und JXX´ which are derived from parameters K and M.
Hence direct analysis of an [AX]2 spectrums yields several solutions for coupling constants.
This problem may be overcome in practice by comparison of well-known coupling constants

from structurally related model systems (or by double resonance).
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8.9.1 Practical Examples for Heteronuclear [AX]2 Cases
8.9.1.1 Fluorinated Ethylenes C2 H4-x Fx (x = 1 - 3), Solutions in c-C6 H12.
Coupling Constants nJHH, nJFH, nJFF (n = 2, 3)
H H H F F F H F F F
C C C C C C C C C C
H F H F H H F H F H
J Type CH2=CHF CH2=CF2 CHF=CHF CHF=CHF CHF=CF2

gem cis trans -
ABCX [AX]2 [AX]2 [AX]2 AXYZ
2
JHH gem -3.06 -4.60 - - -
3
JHH cis +4.07 - -2.07 - -
3
JHH trans +12.68 - - +9.53 -
2
JFH gem +84.67 - +71.84 +75.10 +70.56
3
JFH cis +19.63 +0.64 - +2.80 -4.19
3
JFH trans +151.81 +33.90 +19.77 - +12.52
2
JFF gem - +30.93 - - x
3
JFF cis - - -19.04 - x
3
JFF trans - - - -133.46 x
x)
Data from literature not yet found.
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The Cis-1,2-difluoroethylene Problem
50 40 30 20 10 0 -10 -20 -30 -40 -50

[Hz]
Figure 269 : A or X part of the [AX]2 spectrum from cis-difluoroethylene. Central frequency arbitrarily
chosen to 0 Hz.
Decomposition of the [AX]2 Spectrum
K L2 + K2
M L2 + M2
50 40 30 20 10 0 -10 -20 -30 -40 -50

[Hz]
Figure 270 : Decomposition of the [AX]2 spectrum from cis-difluoroethylene.
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Exercise 1:
Which of the Difluoroethylenes C2H2F2 is it?
H F F F H F
C C C C C C
H F H H F H
Evaluate the following [AX]2 spectrum and the list of transition frequencies and intensities.
40 20 0 -20 -40
(Hz)
Figure 271 : [AX]2 spectrum. Find the molecular structure of this isomer of C2H2F2.

[Hz] [rel]
1 -46.878 0.223
2 -38.886 0.308
3 -17.300 4.000
4 -7.086 1.692
5 -5.878 1.777
6 5.878 1.777
7 7.086 1.692
8 17.300 4.000
9 38.886 0.308
10 46.878 0.223
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Exercise 2:
A hypothetical [AX]2 spectrum - simulated for didactical purposes. Parameters are shown below:
Parameters [Hz] Parameters [Hz]
νA 15
νX -15
JAX 4 N 11
JAX´ 7 L -3
JAA´ 1.5 K 4
JXX´ 2.5 M -1
30 25 20 15 10 5 0 -5 -10 -15 -20 -25 -30

[Hz]
A part X part
Figure 272 : A hypothetical [AX]2 spectrum.
Inspect and reanalyze this spectrum.
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Limiting Cases of the [AX]2 System
Discuss and construct corresponding spectra for some particular situations of [AX]2 systems. We
may find 10 to 3 lines for the A part (and the X part) of [AX]2 spectra.
Lines Pattern Parameters

10 standard [AX]2 spectrum Normal spectra.
None of subsequent rules are valid.
9 Two ab sub-spectra and N = 0; (L, K, M) ≠ 0.
one strong line at νA.
8 One ab sub-spectrum yielding M and L and a) K = 0
four lines (2:1:1:2 or 1:2:2:1) yielding N and L.
8 One ab sub-spectrum yielding K and L and b) M = 0
four lines (2:1:1:2 or 1:2:2:1) yielding N and L.
6 One ab sub-spectrum yielding L, K, M and a) K = M
one doublet yielding N.
6 One ab sub-spectrum yielding L, K, M and b) K = M << L = N
one doublet yielding N.
Spectrum appears as a distorted triplet.
5 Four lines (2:1:1:2) yielding N and L a) M = 0 and K >> L
and one central line (2). which is equivalent to:
A 5-line pattern with intensities 2:1:2:1:2. JAX ~ JAX´ and JAA´ = JXX´ .
5 Four lines (2:1:1:2) yielding N and L b) K = 0 and M >> L
and one central line (2). which is equivalent to:
A 5-line pattern with intensities 2:1:2:1:2. JAX ~ JAX´ and JAA´ = JXX´ .
4 Four lines (1:1:1:1) K = M = 0 and 0 ≠ N ≠ L ≠ 0.
Separation of outer lines yields N or L. This implies:
Separation of inner lines yields L or N. JAA´ = JXX´ = 0
3 Three lines (1:2:1) a) L = 0
Separation of outer lines yields N.
Deceptively simple triplet.
3 Three lines (1:2:1) b) |L| « |K| and |L| « |M| and N ≠ 0.
Separation of outer lines yields N. A more accurate description is:
Deceptively simple triplet.
L2 or L2
≤ HWB ≤ HWB
2K 2M
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8.9.1.2 Some Symmetrically Substituted Fluorinated Benzenes of Type C6H2F2R2.
H F
F R H R
F R H R
H F
R R R
F H H H F H
F H F F H F
R R R
R = Cl, Br, OMe
1 19
We have studied the H and F NMR spectra of a variety of compounds from the above described
series, hoping to get some useful representatives for standard [AX]2 spectra. Surprisingly
deceptively simple [AX]2 spectra appearing as primitive triplets were observed, which by direct
analysis solely yield the resonance frequencies νH and νF and the absolute value ІNІ. Individual
n n n
coupling constants JHH, JFH, JFH (n=3-5) are not accessible. In an advanced chapter on 5-spin
13 1 19
systems some solutions to those problems via C satellites in H and F NMR spectra or
13
C NMR spectra are described.
Problem:
19 1 1 19
What do you see in proton-decoupled F{ H} and fluorine-decoupled H{ F} NMR spectra? What
13 19 1 1 19
do you extract from C satellites in F{ H} and H{ F} NMR?
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1,2-Dibromo-4,5-difluorobenzene
7.50 7.49 7.48 7.47 7.46 7.45 -136.20 -136.22 -136.24

1 19
500 MHz H NMR. HWB = 0.80 Hz. 470 MHz F NMR. HWB = 1.05 Hz.
Br
H Br
F H
F
-136.10 -136.20 -136.30 -1
19 1
1,2-dibromo-4,5- difluorobenzene Proton-decoupled 470 MHz F{ H} NMR
Figure 273 : NMR spectra of 1,2-dibromo-4,5-difluorobenzene.
NMR Data of 1,2-Dibromo-4,5-difluorobenzene.
Parameter Spins Data

δH H3, H6 7.498 [ppm]
δF F4, F5 -136.309 [ppm]

N 17.10 [Hz]
L 1.90 [Hz]
K -20.40 [Hz]
M 21.00 [Hz]
JFH F4, H3 9.50 [Hz]
JFH F4, H3 7.60 [Hz]
JHH H3, H6 0.30 [Hz]
JFF F4, F5 -20.70 [Hz]
13 1 19 19 1 13 1
Obtained from C satellites in H, F, F{ H} and from C{ H} NMR.
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1,4-Dibromo-2,5-difluorobenzene
7.38 7.37 7.36 7.35 7.34 7.33 -111.42 -111.44 -111.46 -11
1 19
500 MHz H NMR. HWB = 0.56 Hz. 470 MHz F NMR. HWB = 0.64 Hz.
Br
H F
F H
Br -111.40 -111.50
19 1
1,4-dibromo-2,5- difluorobenzene Proton-decoupled 470 MHz F{ H} NMR
Figure 274 : NMR spectra of 1,4-dibromo-2,5-difluorobenzene.
NMR Data of 1,4-Dibromo-2,5-difluorobenzene
Parameter Spins Data

δH H3, H6 7.348 [ppm]
δF F2, F5 -111.522 [ppm]
N 13.40 [Hz]
L 1.6 [Hz]
K 13.7 [Hz]
M -13.1 [Hz]
JFH F2, H3 7.50 [Hz]
JFH F2, H6 5.90 [Hz]
JHH H3, H6 0.30 [Hz]
JFF F2, F5 13.40 [Hz]
13 1 19 19 1 13 1
Obtained from C satellites in H, F, F{ H} and C{ H} NMR.
Data from: J. H. Kühn-Velten; PhD Thesis, Heinrich-Heine-University Düsseldorf, 2005.
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8.9.2 Practical Examples for Homonuclear [AX]2 Cases
1 19
8.9.2.1 Practical Example 1: The Fluorine-decoupled 500 MHz H{ F} NMR Spectrum of
4-Fluorobenzoic Acid.
COOH
H H
H H
F
4000 3900 3800 3700
(Hz)
Figure 275 : 500 MHz 1H{19F} NMR spectrum of 4-fluorobenzoic acid.
4072 4068 4064 4060 4056

(Hz)
Figure 276 : The A part simulated with HWB = 0.1 Hz.
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3652 3648 3644 3640

(Hz)
Figure 277 : The X part simulated with HWB = 0.1 Hz.
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1 19
The Fluorine-decoupled 500 MHz H{ F} NMR Spectrum of 4-Fluorobenzoic Acid

1 4072.0230 0.4663
2 4069.1659 1.9569
3 4069.1590 1.9570
4 4069.0797 0.9165
5 4068.5489 1.0438
6 4067.0009 1.4995
7 4062.3083 1.5335
8 4060.7457 1.0835
9 4060.2149 0.9562
10 4060.1433 2.0431
11 4060.1356 2.0432
12 4057.2862 0.5004
13 3653.3278 0.5004
14 3650.4784 2.0432
15 3650.4707 2.0431
16 3650.3991 0.9562
17 3649.8683 1.0835
18 3648.3057 1.5335
19 3643.6131 1.4995
20 3642.0651 1.0438
21 3641.5343 0.9165
22 3641.4550 1.9570
23 3641.4481 1.9569
24 3638.5910 0.4663
Remarks: In practice many homonuclear systems, expected to be [AX]2, may show minor [AB]2
1 19
character. E. g.: Even at 500 MHz the H{ F} NMR spectrum of 4-fluorobenzoic acid exhibits
some [AB]2 features as indicated by a total of 24 lines and a weak roof effect for the N-lines (marked
bold black in the table shown above).
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Corresponding parameters for 4-fluorobenzoic acid are listed below:
Parameters Parameters [Hz]

ν1 = ν 2 4064.606
ν3 = ν 4 3646.008
4
J12 JHH(meta) 2.777
3
J13 =J24 JHH(ortho) 8.670
5
J14 =J23 JHH(para) 0.353
4
J34 JHH(meta) 2.246
Remember: [AX]2 analysis of a homonuclear [AX]2 spin system does not allow to assign
unequivocally the resonances νA and νX to stereo specific positions of nuclei. In the present
situation this implies, that we do NOT know if νA is ortho to the COOH- or ortho to the F-substituent
1
in 4-fluorobenzoicacid. This problem is solved by inspecting the fluorine coupled H NMR
spectrum (which will be discussed in a chapter on 5-spin systems). The low-field A-protons are meta
4 3
to fluorine ( JFH = 5.519 Hz) while the high-field X-protons are ortho to fluorine ( JFH = 8.786 Hz).
Expectation Values for Coupling Constants [Hz] in Benzene Derivatives
C6HxFy (x+y = 6)
ortho meta para
JHH 7.5 to 9.1 0.8 to 3.1 0.0 to 0.9
JFH 7.6 to 10.5 3.2 to 8.7 -2.7 to -0.2
JFF -18.8 to -20.6 -1.4 to 6.6 8.6 to 17.8
C6H2F2RR´ (R, R´ = Br, Cl, COOH, OCH3)
ortho meta para
JHH 2.9* 0.3 to 0.4
JFH 9.5 to 12.5 5.9 to 8.6 -1.9*
JFF -20.7 to -21.4 - 13.4 to 16.7
C6HxFy(SCH3)z (x+y+z = 6)
ortho meta para
JHH 7.5 to 9.3 1.6 to 3.0 0.2
JFH 7.6 to 10.8 3.8 to 8.6 -2.6 to -1.3
JFF -20.9 to -26.5 -1.4 to 7.2 9.0 to 16.1
In favorable cases AA´ and XX´ spins may be assigned by computational chemical shift
prediction. See specific references for this topic.
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Some Suggestions for Reading
a) http://www.modgraph.co.uk/product_nmr_charge.htm
b) Banfi, D.; Patiny, L. www.nmrdb.org: Resurrecting and processing NMR spectra on-line Chimia,
62, 280-281 (2008).
c) Y. Binev, J. Aires-de-Sousa, "Structure-Based Predictions of 1H NMR Chemical Shifts Using
Feed-Forward Neural Networks", J. Chem. Inf. Comp. Sci., 44, 940-945 (2004).
d) Y. Binev, M. Corvo, J. Aires-de-Sousa, "The Impact of Available Experimental Data on the
Prediction of 1H NMR Chemical Shifts by Neural Networks", J. Chem. Inf. Comp. Sci., 44, 946-
949 (2004).
e) Aires-de-Sousa, M. Hemmer, J. Gasteiger, “Prediction of 1H NMR Chemical Shifts Using Neural
Networks”, Analytical Chemistry, 74, 80-90 (2002).
3
f) P. S. Beauchamp, R. Marquez, “Estimation of sp Chemical Shifts. A General Approach for
Calculating Proton Chemical Shifts for Methyl, Methylene, and Methine Protons When There
Are One or More Substituents within Three Carbons”, J. Chem. Ed., 74, 1483-1485 (1997).
g) J. Beeby, S. Sternhell, T. Hoffmann-Ostenhof, E. Pretsch, W. Simon, "Estimation of the
Chemical Shifts of Aromatic Protons Using Additive Increments", Anal. Chem. 45, 1571-1573
(1973).
h) U. E. Mater, C. Pascual, E. Pretsch, A. Pross, W. Simon, S. Sternhell, "Estimation of the
chemical shifts of olefinic protons using additive increments - II. The compilation of additive
increments for 43 functional groups", Tetrahedron 25, 691-697 (1969).
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19
8.9.2.2 Practical Example 2: 470 MHz F NMR Spectrum of 1,2-Dibromo-tetrafluorobenzene
(10% in CD3CN).
While o-C6H4Br2 gives rise to an [AB]2 system, o-C6F4Br2 approximates [AX]2.
25 15 5 -5 -15 -25 -35

(Hz)
19
Figure 278 : 470 MHz F NMR spectrum of 1,2-dibromo-tetrafluorobenzene.
F
ν1 = ν 4 νF 0.0 by def.
F Br J12 = J34 JAX = JA´X´ -21.0
J13 = J23 JAX´ = JA´X 3.0
F Br J14 JAA´ 7.9
F J23 JXX´ -19.1

1 31.5796 0.2507
2 18.8520 0.5745
3 9.0173 1.9957
4 9.0097 1.9957
5 7.6521 1.4203
6 4.5797 1.7455
7 -4.5452 1.7493
8 -7.6326 1.4255
9 -8.9828 2.0043
10 -8.9903 2.0043
11 -18.8326 0.5797
12 -31.5451 0.2545
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1
8.9.2.3 Practical Example 3: Comparison of 60 MHz and 500 MHz H NMR Spectra from
γ-Pyrone (30% in CCl4).
E. W. Garbisch Jr. described the 60 MHz H NMR spectrum of γ-Pyrone (30% in CCl4) and analyzed
1
it as [AX]2 system. Read: J. Chem. Educ. 45, 480-493 (1968).
Parameter [Hz]
O
νA = νA´ 477.00
H H A A´ νX = νX´ 378.00
J12 = J34 5.87
J13 = J24 0.40
H O H X X´ J14 2.68
J23 1.15
HWB 0.20
480 460 440 420 400 380 360

(Hz)
1
Figure 279 : 60 MHz H NMR spectrum
The 60 MHz spectrum shows some [AB]2 character as easily visible by the “roof-effect” of the N-
lines.
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484 480 476 472 468

(Hz)
384 380 376 372

(Hz)
1
Figure 280 : 60 MHz H NMR spectrum. Upper: A part. Lower: X part.
A Part X Part
Line Frequency Intensity Line Frequency Intensity
1 482.3465 0.3838 13 383.1481 0.4744
2 480.6793 0.6787 14 381.5283 0.7850
3 480.2342 1.8736 15 381.0615 2.1282
4 480.2128 1.8747 16 381.0358 2.1264
5 479.1517 1.2150 17 380.0006 1.3213
6 478.5208 1.5245 18 379.3225 1.6144
7 475.6775 1.6144 19 376.4792 1.5245
8 474.9994 1.3213 20 375.8483 1.2150
9 473.9642 2.1264 21 374.7872 1.8747
10 473.9385 2.1282 22 374.7658 1.8736
11 473.4717 0.7850 23 374.3207 0.6787
12 471.8519 0.4744 24 372.6535 0.3838
Note: N-lines split into two components.
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The 500 MHz spectrum of γ-Pyrone exhibits [AX]2 character as demonstrated in the figure below:
3984 3980 3976 3972 3968

(Hz)
3156 3152 3148 3144

(Hz)
Figure 281 : 500 MHz H NMR spectrum. Upper: A part (νA = 3975 Hz).Lower: X part. (νX = 3150 Hz).
1
A Part X Part
1 3980.2656 0.4210 13 3155.2418 0.4319
2 3978.6140 0.7243 14 3153.5959 0.7370
3 3978.1469 1.9848 15 3153.1260 2.0152
4 3978.1441 1.9848 16 3153.1231 2.0152
5 3977.0841 1.2630 17 3152.0659 1.2757
6 3976.4357 1.5681 18 3151.4118 1.5789
7 3973.5882 1.5789 19 3148.5643 1.5681
8 3972.9341 1.2757 20 3147.9159 1.2630
9 3971.8769 2.0152 21 3146.8559 1.9848
10 3971.8740 2.0152 22 3146.8531 1.9848
11 3971.4041 0.7370 23 3146.3860 0.7243
12 3969.7582 0.4319 24 3144.7344 0.4210
Note: For homonuclear [AX]2 cases N-lines split into two components, even at 500 MHz.
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8.9.2.4 Practical Example 4: An [AX]2 System Monitored by Proton-decoupled 202 MHz

31 1
P{ H} NMR.
A Bis-pentacarbonylchromium(0) Complex of Tetrakis-c-hexyl-cyclotetraphosphine:
Parameter [Hz]
R Cr(CO)5
νA 12850.4890
(OC)5Cr R νX -3845.6338
P P
JAX = JA´X´ -154.7000
P P JAX´ = JA´X 94.4000
R
JAA´ -118.0900
R
JXX´ -113.3500
13050 12900 12750 12600

(Hz)
Figure 282 : A part. Digital resolution is 7.5 Points/Hz.
-3600 -3750 -3900 -4050

(Hz)
Figure 283 : X part. Digital resolution is 7.5 Points/Hz.
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A Part X Part
1 13136.2454 0.3087 13 -3559.9862 0.3306
2 12978.3603 0.9661 14 -3719.6206 0.9959
3 12973.6209 1.0041 15 -3724.3601 1.0339
4 12904.8344 1.6698 16 -3791.3973 1.6916
5 12881.5827 1.9925 17 -3815.5383 2.0072
6 12880.6934 1.9928 18 -3816.3987 2.0069
7 12821.2538 2.0069 19 -3875.8383 1.9928
8 12820.3934 2.0072 20 -3876.7276 1.9925
9 12796.2525 1.6916 21 -3899.9792 1.6698
10 12729.2152 1.0339 22 -3968.7657 1.0041
11 12724.4758 0.9959 23 -3973.5052 0.9661
12 12564.8414 0.3306 24 -4131.3903 0.3087
Parameter [Hz]
∆ν 16,696.13
N 60.30
L -249.10
K -231.44
M -4.74
Look at the two expanded spectra for A and X parts shown above. A weak “roof effect” is
discovered. But surprisingly a large spectral relation ∆ν/N of 277 is calculated. The total
31 1
heteronuclear P{ H} NMR spectrum was simulated (for both A- and X-nuclei simultaneously) with
a digital resolution of 7.5 Points/Hz.
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But if the digital resolution is enhanced to 216 Points/Hz by simulating specific A- or X-regions only,
the spectral habitus changed to the following graphics:
13100 13000 12900 12800 12700 12600

(Hz)
Figure 284 : A part. Digital resolution is 216 Points/Hz.
-3600 -3700 -3800 -3900 -4000 -4100

(Hz)
Figure 285 : X part. Digital resolution is 216 Points/Hz.
This phenomenon is commonly observed in heteronuclear NMR – if insufficient digital resolutions

are induced (involuntarily).
Remember: A “good” spectrum should have > 15 points per spectral half width.
Summing up: In all four examples for homonuclear [AX]2 systems corresponding spectra showed
some [AB]2 characters. Hence it is advisable to perform a direct [AX]2 analysis but continue
with the full [AB]2 iteration.
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8.9.3 [AX]2 Systems with Rare Nuclei in Inorganic Chemistry
15
The N isotopomer of difluorodiazine exists in cis and trans forms which give rise to two distinct
13
[AX]2 spectra. Another significant [AX]2 spectrum was obtained from the C isotopomer of
oxalylfluoride.
F O F
15 15 15 15 13 13
N N N N C C
F F F F O
1 2 3
Parameters Type 1 2 Type 3

δF 137.15 94.82 23.8 ppm
N -185.6 -110.0 -263.13 Hz

L -236.4 -235.6 -467.23 Hz
K -142.0 -297.9 179.17 Hz
M -150.0 -234.9 72.61 Hz
1 1
JAX JFN -211.0 -172.8 JFC -365.18 Hz
2 2
JAX´ JFN +25.4 +62.8 JFC +102.05 Hz
1 1
JAA´ JNN -146. -316.4 JCC +125.89 Hz
3 3
JXX´ JFF +4.0 +18.5 JFF +53.28 Hz
For details read:

a) F. Aubke, G. Hägele, H. Willner; Magn. Res. Chem. 33, 817-822 (1995).
b) H. Pernice, H. Willner, R. Eujen; J. Fluorine Chem. 112, 277-281 (2001).
Remark: Theory and applications of [AX]2 and [AX]2 spectra were described in a review
“Protonenresonanzspektren vom AA´XX´- und AA´BB´-Typ - Analyse und Systematik” by
H. Günther; Angew. Chem. 84, 907 (1972); Angew. Chem. Int. Ed. Engl. 11, 861 (1972).
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8.10 The AXX´2 System – Spin System No. 28
1 1 19
The H NMR spectrum of 1,3,5-trichlorobenzene and the fluorine decoupled H{ F} NMR spectrum
12
of 1,3,5-trifluorobenzene 2 consists basically of a singlet due to the all- C-isotopomeric molecules,
contributing 93.7 % to the total intensity. Expanding the intensity scale reveals two different sets of
13
C satellites, with statistical weights of 3.3 % each, corresponding to isotopomers 1a, 1b, 2a, and
2b shown below:
1 2 1a and 2a 1b and 2b
A3 [AM]3 AA´2X AA´2X
1 1 19
H NMR of 1,3,5-trichlorobenzene 1 and fluorine decoupled H{ F} NMR
of 1,3,5-trifluorobenzene 2 with isotopomers 1a, 2a, 1b, and 2b.
1 12
The H NMR spectrum of 1,3,5-trifluorobenzene is more complex. The all- C-isotopomer builds up
93.7 % of total intensity as an [AX]3 system, which will be mentioned in a later chapter on 6-spins.
Decoupling the protons reduces the problem to
2c 2d
MM´2X to MN2X MM´2X to MN2X
1 1 19 19 19 1 13 1 13 19
An excellent paper reported the result from H, H{ F}, F, F{ H}, C{ H}, and C{ F} spectra
and corresponding analysis for 1,3,5-trifluorobenzene. Details will be discussed at the end of this
chapter.
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8.10.1 Practical Example: An AXX´2 Spin System with A = 13C; X, X´ = 31P
-
Tripod ligands [CpM(P(O)R2)3] (Cp = C5H5; M = Co, Rh, Ir; R = O-alkyl, O-aryl, alkyl, aryl) exhibit
threefold symmetry (assuming free rotation for the Cp substituent at ambient temperature).
31 1 13 1
The proton decoupled P{ H} NMR spectrum shows a singlet, while the proton decoupled C{ H}
13 31
NMR spectrum exhibits a special case of the AXX´2 spin system (A = C; X, X´ = P). The coupling
pattern is described by:
We will use this example to develop equations for transitions frequencies and intensities and
discuss the general pattern of the AXX´2 case, including some limiting situations.
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The A Part
The A part of the AA´2X system consists of 12 lines, symmetrically centered in 6 pairs around νA
Figure 286 : A part of AXX´2. Simulation with parameters: νA = 0 Hz. JAX = 100 Hz. JAX´ = 5 Hz. JXX´= 50
Hz. For line numbering f1 to f12 see chapter 8.10.2.
The coupling constant JAX´ is found as a 6-fold repeated spacing. The sum of coupling constants
JAX+JAX´ appears twice. The inner and outer separations between the 4 strongest lines (of unit
intensity) correspond to JAX and JAX+2JAX´resp.. Furthermore two repeated spacings are found -
each 4 times - abbreviated with 2x and 2y, which are defined by:
1
[1] =
x (JAX + JXX´ − JAX´ )2 + 8 J2XX´
4
1
[2] =
y (JAX − JXX´ − JAX´ )2 + 8 J2XX´
4
We easily recognize the AB type pattern with two “outer lines” separated by 4x and two “inner lines”
separated by 4y. The absolute value of JXX´ is obtained from the A part by:
(2x)2 − (2y)2
[3] JXX´ =
JAX − JAX´
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The XX´2 Part
The XX´2 part consists of 18 lines, symmetrically arranged in pairs around νX. We do not need to
analyze those 18 lines in details. The center is νX.
5120 5080 5040 5000 4960 4920 4880

(Hz)
Figure 287 : XX´2 part of AXX´2.
Compare the A and the XX´2 part (red arrows). We could extract absolute values for 2x, 2y, JAX,
and JAX´ from the XX´2 part, but don’t need to do it.
5120 5080 5040 5000 4960 4920 4880

(Hz)
Figure 288 : Comparison of A and XX´2 parts. Upper: A part. Lower: XX´2 part.
For completeness sake: What do we see in the XX´2 part? The overlap of two xy2 type sub-spectra.
Both sub-spectra are mirror images to each other.
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Effective Larmor frequencies are given by:
1
[4] ν x1 =ν X + JAX
2
1
[5] ν x2 =ν X − JAX
2
1
[6] ν y1 =ν X + JAX´
2
1
[7] ν y2 =ν X − JAX´
2
After analyzing those two sub-spectra, νX, JXX´, JAX, and JAX´ are found. For help see chapter on
AB2X spectra (8.8.1).
Remarks from Composite Particle Theory
The AXX´2 system can be broken down into DADXSX2 and DADXTX2. Hence an ax type sub-spectrum
(DADXSX2) must be found in the A and in the XX´2 part as well yielding directly νA, νX and JAX.
Indeed, the “inner lines” (of unit intensity) from the A part are centered symmetrically around νA and
are separated by JAX.
Relative Signs of Coupling Constants
Neither the sign of JXX´ nor the sign of N = (JAX + JAX´) affect the spectral appearance of AXX´2. But
changing one sign for JAX or JAX induces a different pattern in both the A and the XX´2 part.
Special Cases of the AXX´2 System
Case Conditions
1 JXX´ = 0
2 JAX = 0
3 JAX = 0 and |JAX| << |JxX|
4 JAX = 0 and |JAX| << |JxX|
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Simulations
Case JAX JAX´ JXX´

1 100 5 0
2 100 0 50
3 10 0 50
4 100 0 5
Case 1
120 80 40 0 -40 -80 -120

(Hz)
Figure 289 : Case 1: A part. Doublet by JAX, triplet by JAX´
5120 5080 5040 5000 4960 4920 4880

(Hz)
Figure 290 : Case 1: XX´2 part. Weaker doublet by JAX, stronger doublet by JAX´
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Case 2
120 80 40 0 -40 -80 -120

(Hz)
Figure 291 : Case 2: A part. Strong doublet by JAX.
5120 5080 5040 5000 4960 4920 4880

(Hz)
Figure 292 : Case 2: XX´2 part. Red arrows: doublet by JAX.
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Case 3
120 80 40 0 -40 -80 -120

(Hz)
Figure 293 : Case 3: A part. Outer lines: JAX. Inner lines: 1/3 JAX.
5120 5080 5040 5000 4960 4920 4880

(Hz)
Figure 294 : Case 3. XX´2 part.
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Case 4
120 80 40 0 -40 -80 -120

(Hz)
Figure 295 : Case 4: A part. Doublet by JAX.
5120 5080 5040 5000 4960 4920 4880

(Hz)
Figure 296 : Case 4. XX´2 part.
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Coming Back to Practice
13 1
The proton decoupled 50.323 MHz C{ H} spectrum for the methoxy region of the tripod ligand
-
[CpCo{P(O)(OCH3)2}3] is shown below.
13 1 -
Figure 297 : 50.323 MHz C{ H} spectrum of [CpCo{P(O)(OCH3)2}3] .
In this example we recognize special case 3 of the AXX´2 problem. Hence only two parameters are
accessible: νA( C) = 2594.02 Hz and | JPC | = 8.37 Hz.

13 2
Further examples for AXX´2 systems occur for spectra of compounds like
13 13 1 13 19
1,3,5-trichlorobenzene ( C), 1,3,5-trifluorobenzene ( C{ H}, C{ F}) and the following
13 1
phosphorous compounds ( C{ H}):
13 19 1
Read: “The Complete C, F and H Spectral Analysis of the fluorobenzenes C6HnF6-n. I. 1,3,5-
Trifluorobenzene” from V. Wray, D. N. Lincoln;. J. Magn. Res. 18, 375-382 (1975).
12
The all- C-isotopomer 1,3,5-C6H3F3 is described by two resonance frequencies and four coupling
constants forming an [AX]3 spin system.
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Parameter [Hz] Reference

νH 661.90 TMS
νF 5320.81 C6F6
3
JFH(ortho) 9.1215
5
JFH(para) -1.6818
4
JHH(meta) 2.3033
4
JFF(meta) 5.8275
13 19 13
Decoupling the fluorines in C{ F} leads to the overlay of two C-isotopomers:
An AXX´2 System with Very Weak AXY2 Character
Parameter [Hz]
νC A 4145.07
νH X 661.90-0.20
νH X´2 661.90-0.27
2
JCH(ortho) JAX -5.96
4
JCH(para) JAX´ -0.34
4
2a JHH(meta) JXX´ 2.30
An AXX´2 System with Very Weak AX2Y Character
Parameter [Hz]
νC A 2539.67
νH X 661.90-0.41
νH X´2 661.90-0.25
1
JCH(ipso) 168.28
3
JCH(meta) 4.29
4
2b JHH(meta) 2.31
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Corresponding Spectra for AXX´2 Approximations of Isotopomer 2a
4152 4148 4144 4140 4136

(Hz)
13 19
Figure 298 : C{ F} of isotopomer 2a. A part of AXX´2 .
670 668 666 664 662 660 658 656 654

(Hz)
13 1 19
Figure 299 : C satellites in H{ F} of isotopomer 2a. XX´2 part of AXX´2.
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Corresponding Spectra for AXX´2 Approximations of Isotopomer 2b
2600 2560 2520 2480

(Hz)
13 19
Figure 300 : C{ F} of isotopomer 2a. A part of AXX´2.
720 680 640 600

(Hz)
13 1 19
Figure 301 : C satellites in H{ F} of isotopomer 2b. XX´2 part of AXX´2.
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Corresponding Spectra for AXY´2 of Isotopomer 2a
4152 4148 4144 4140 4136

(Hz)
13 19
Figure 302 : C{ F} of isotopomer 2a. A part of AXY´2.
670 668 666 664 662 660 658 656 654

(Hz)
13 1 19
Figure 303 : C satellites in H{ F} of isotopomer 2a. XY´2 part of AXY´2.
13
Remember: C-isotopomer effects reduce the symmetry of molecule and spin system.
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Corresponding Spectra for AX2Y of Isotopomer
2600 2560 2520 2480

(Hz)
13 19
Figure 304 : C{ F} of isotopomer 2b. A part of AX2Y .
720 680 640 600

(Hz)
13 1 19
Figure 305 : C satellites in H{ F} of isotopomer 2b. X2Y part of AX2Y.
13
Remember: C-isotopomer effects reduce the symmetry of molecule and spin system. Possibly not
easily visible in some spectra but found by iteration.
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Four-Spin Systems
12 13 13 1
The C/ C-isotope effect is even stronger for the fluorine spins in the proton decoupled C{ H}
13 19 1
spectrum and in the C satellites of the F{ H} spectrum. Hence AX2Y and AXY2 spectra are
observed. Simulate those spectra with TopSpin / DAISY using the following data:
AX2Y System
Parameter [Hz]
νC A 2539..67
νF X 5320.81-0.74
νF X´2 5320.81-2.53
2
JFC(ortho) JAX 25.908
4
JCF(para) JAX´ 4.339
2b 4
JFF(meta) JXX´ 5.849
AXY2 System
Parameter [Hz]
νC A 4145.07
νF X 5320.81-8.79
νF X´2 5320.81-0.65
1
JFC(ipso) JAX 248.63
2
JFC(meta) JAX´ 15.39
4
2a JFF(meta) JXX´ -5.82
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8.10.2 Explicit Equations for Transition Frequencies and Intensities were

Derived
The A Part
No Frequency Intensity
The X Part
No Frequency Intensity
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Four-Spin Systems
The calculation of transition frequencies is straightforward. Intensities are accessible after some
trigonometric considerations. Auxiliary angles θ, φ, and linear combinations (θ + φ), and (θ – φ) can
be derived from:
1
[31] =
x (JAX + JXX´ − JAX´ )2 + 8 J2XX´
4
1
[32] =
y (JAX − JXX´ − JAX´ )2 + 8 J2XX´
4
JAX + JXX´ − JAX

[33] cos 2θ =
(JAX + JXX´ − JAX´ )2 + 8 J2XX´
JXX´
[34] sin 2θ = 2
(JAX + JXX´ − JAX´ )2 + 8 J2XX´
JAX − JXX´ − JAX

[35] cos 2ϕ =
(JAX − JXX´ − JAX´ )2 + 8 J2XX´
JAX´
[36] sin 2ϕ = 2
(JAX − JXX´ − JAX´ )2 + 8 J2XX´
For details see: H. Dolhaine, R. Fuhler, G. Hägele, W. Kläui; Z. f. Naturforsch. 50b, 1665-1672
(1995).
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8.11 The A2X2 System – Spin System No. 30
Homonuclear A2X2 systems spectra are found in high field spectra of cylopropene 1,
perfluorocyclopropene 2, while heteronuclear A2X2 systems are represented by
difluorocyclopropenes 3 and 4 (difluorocyclopropene 5 gives rise to an AMRX system).
H F
C C
H H
C C C C
H H F F
1 2
H F F
C C C
H F H
C C C C C C
F F H H H F
3 4 5
Further heteronuclear A2X2 systems are represented by methylenedifluoride CH2F2, difluoroallene 6
H F H F
C C C C
H F F
H
6 7
4- 4-
and the anions [O3P-CH2-PO3] 8 and [O3P-CF2-PO3] 9.
F C F
CH2F2 shown in this projection H will be used as a model.
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Four-Spin Systems
A 1 A
X X 3 4 X X
A 2 A
The analysis of an A2X2 spectrum is straightforward. Two congruent triplets are observed, each
centered around νA or νX resp.. JAX is found four times, twice in each of those triplets. Triplets
occur with intensities 1:2:1 hence following Pascal´s numbers.
Intensity A 2X 2
νA νX
1
∆ν
0.8
0.6
JAX
0.4
0.2
0
20+ νA -20 20+ νX -20
Figure 306 : Simulated A2X2 spectrum
Within this four spin systems the following symmetry criteria hold:
[1] ν1 =ν 2 =ν A
[2] ν3 =ν 4 =ν X
[3] J=
13 J=
14 J=
23 J=
24 JAX
The pairs of A- and X-nuclei are magnetically equivalent and form composite particles A2 and X2
resp..
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Two single spins with I = ½ form a composite particle A2 with a total spin Itot:
[4] Itot = 2*I = 1
The composite particle can be subdivided in two actual spin components Iact:
Iact = 1 the triplet-state 1TA of the A2 particle

2
Iact = 0 the singlet state 0SA of the A2 particle

2
Both states occur with identical statistical weight.

Analogous conclusions (1TX , 0SX ) hold for the X2 particle.
2 2
Hence the total four spin systems may be described by four combinations:
1. The combination 0SA 0SX is totally spin-inactive and does not give rise to transitions in
2 2
the NMR spectrum.

2. The combination 1TA 0SX may be regarded as an X-decoupled spectrum of an A2X2
2 2
system connected with a transition at νA of unit intensity.
3. The combination 0SA 1TX is analogous to 1TA 0SX , hence connected with a
2 2 2 2
transition centered around νX of unit intensity.
4. The combination 1TA 1TX gives rise to two triplets of unit intensities. Triplets are
2 2
centered around νA and νX resp.. From those 6 lines four repeated spacings are
extracted with absolute values for JAX.
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Four-Spin Systems
Decomposition of Total Spectrum A2X2 into Sub-spectra
νA νX
50 -50 -150
(Hz)
Figure 307 : 1TA 0SX and 0SA 1TX
2 2 2 2
JAX
 
 
50 -50 -150
(Hz)
Figure 308 : 1TA 1SX

2 2
50 -50 -150
(Hz)
Figure 309 : The total spectrum consists of sub-spectra 1TA 0SX , 0S 1

A 2 TX 2 , 1T 1
A 2 TX 2
2 2
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Practical Examples as Shown Above
a homonuclear cases c-C3H4, c-C3F4

4- 4-
b heteronuclear cases c-C3H2F2, [O3P-CH2-PO3] , [O3P-CF2-PO3] , CH2F2
Be aware: Deceptively simple [AX]2 spectra appear like simple A2X2 spectra.
See the 500 MHz spectrum of β-bromopropionic acid Br-CH2-CH2-COOH in CDCl3:
s a e u r e
3.5904
3.5768
3.5633
3.0102
2.9967
2.9832
3.5904
3.5768
3.5633
3.0102
2.9967
2.9832
54 . 03 . 53 . 02 3 .6 0 0 3 .5 8 5 3 .5 7 0 3 .5 5 5 3 .0 3 0 3 .0 1 5 3 .0 0 0 2 .9 8 5 2 .9 7 0
( p p m ) (p p m ) (p p m )
a b c
Figure 310 : a) Overview. b) The high frequency A part. c) The low frequency X part.
The homonuclear example of β-bromopropionic acid shows a (very) weak roof effect indicating
some deceptively simple [AB]2 character. The triplet splitting corresponds to N/2 where N = JAX +
JAX´ or N = JAB + JAB´resp.. N = 13.5 Hz was obtained from A and X parts. This indicates: L = JAX -
JAX´ or L = JAB - JAB´ approximates zero.
Read the chapters on [AX]2 and [AB]2 spectra: 8.9 and 8.15.
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Four-Spin Systems
8.12 The AX3 System – Spin System No. 31
For a start a hypothetical spectrum is inspected created from NMR data:
νA = 30 Hz νX = -30 Hz JAX = 10 Hz
This first order system exhibits 6 lines: a quartet for the A and a doublet for the X3 part.
Figure 311 : Simulated AX3 spectrum.
Effective Larmor frequencies and intensities are given by:
3 1
[1] νa1 =ν A + JAX Ia1 = 1 [2] νa2 =ν A + JAX Ia2 = 3
2 2
1 3
[3] νa3 =ν A − JAX Ia3 = 3 [4] νa4 =ν A − JAX Ia4 = 1
2 2
1 1
[5] ν x1 =ν X + JAX Ix1 = 12 [6] ν x2 =ν X − JAX Ix2 = 12
2 2
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Four-Spin Systems
Remember: Relative intensities in a first order multiplet follow Pascal’s numbers. The total intensity
n-1
of an n-spin spectrum is given by n 2 , hence in the AX3 case, 32, divided in a ratio of 8:24 for A
and X3 spins resp.. The experimental ratio of integrals will be 1:3 (or very close to it).
By analysis resonance frequencies follow from
1
[7] ν A= (ν a1 + ν a2 + ν a3 + ν a4 )
4
1
[8] ν X= (ν x1 + ν x2 )
2
The repeated spacing corresponds to the absolute value of the coupling constant J AX
[9] JAX = (ν a1 + ν a2 ) = (ν a2 + ν a3 ) = (ν a3 + ν a4 ) = (ν x1 + ν x2 )
8.12.1 Practical Examples – Part 1
Homonuclear systems CH3CHO, CH3-CHCl2, CH3-CCl2-CHCl2 etc..

Heteronuclear systems CH3F, CH3PCl2, CF3PCl2, PH3, PF3, etc….
Pure acetaldehyde is characterized by an AX3 system with the following NMR data.
a) CH3CHO δH(CH3) : = 2.17 ppm, δH(C(O)H) = 9.72 ppm. 3JHH = 2.7 Hz.
In methanol solution the formation of two different AX3 systems are monitored corresponding to
the CH3CH-fragments of hemi-acetal and the acetal structures:
b) CH3CH(OH)OCH3 δH(CH3) : = 1.29 ppm, δH(CH) = 4.61 ppm. 3JHH = 5.2 Hz.
c) CH3CH(OCH3)2 δH(CH3) : = 1.25 ppm, δH(CH) = 4.63 ppm. 3JHH = 5.2 Hz.
In aqueous solution hydration of the aldehyde function is observed:
d) CH3CH(OH)2 δH(CH3) : = 1.29 ppm, δH(CH) = 5.13 ppm. 3JHH = 5.2 Hz.
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8.12.2 Practical Examples – Part 2
1,1,1-Trifluoromethyl derivatives like CF3H, CF3-CHCl2, CF3-CHBr2, CF3-CHBrCl, CF3-CHR2, and

CF3-C ≡ CH give rise to heteronuclear AX 3 spectra. For CF3-CHR2 (R = 2,4,6-trimethoxyphenyl) the
following parameters were determined:
CH3O H
R
H C CF3 R = OCH3
R
CH3O H
δF = -64.8 ppm (vs. CFCl3). δH = 5.65 ppm (vs. TMS). 3JFH = 11.8 Hz.
Remarks: In addition 3 singlets are found: a) 6 ortho methoxy protons at δH = 3.74 ppm, b) 3 para-
methoxy protons at δH = 3.77 ppm, c) 2 meta protons at 6.09 ppm. Hence the total spectrum
consists of the spectral overlay from the AX3 multiplet and three non-coupled singlets, quite a nice
first order spectrum which can be simulated by TopSpin / DAISY using the fragment technique:
6.0 5.6 5.2 4.8 4.4 4.0

(ppm)
1
Figure 312 : H NMR spectrum of CF3-CHR2 (R = 2,4,6-trimethoxyphenyl). A part of AX3. See the
1 19
expected quartet in H NMR. The F NMR consists of a doublet, not shown here.
A multitude of examples with AX3 systems from inorganic chemistry are found, e.g.: PH3, P(E)F3,
CH3P(E)Cl2, CF3P(E)Cl2 (E= nil, O, S). As an example from coordination chemistry may serve the
complex Cl-Au-PF3: δP = 113.3 ppm. δF = -38.1 ppm. 1JPF = -1357.6 Hz. Solution in C6D6.
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8.13 The ABCD System – Spin System No. 32
The general 4-spin case ABCD may show up with a maximum of 56 lines. At higher fields ABCD
may convert to AMRX exhibiting 32 lines only. Hence the practical ABCD system often will appear
with less than 56 lines in the experimental spectrum.
Practical examples for ABCD systems are found quite frequently in asymmetrically ortho- and meta-
disubstituted benzenes C6H4R R (R
1 2 1
≠ R ) while para-structures will give rise to [AB]
2
2 systems,
which will be dealt with in a separate chapter 8.16.
R1 R1 R1
H R2 H H H H
H H H R2 H H
H H R2
ABCD ABCD [AB]2
1
H spin systems from asymmetrically disubstituted benzenes (R
1
≠ R)2
8.13.1 Example 1: ABCD System in o-C6H4BrCl – 1-Bromo-2-chloro-benzene
Br Br Br
H6 Cl HB Cl HA Cl
H5 H3 HC HA HD HB
H4 HD HC
Spin assignment
I II III
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1
200 MHz H NMR Spectrum of 1-Bromo-2-chloro-benzene in CDCl3 + TMS
7.60 7.50 7.40 7.30 7.20 7.10

(ppm)
1
Figure 313 : 200 MHz H NMR spectrum of 1-bromo-2-chloro-benzene in CDCl3. Upper: experimental.
Lower: iterated.
1
200 MHz H NMR Data for of 1-Bromo-2-chloro-benzene in CDCl3
Parameter Data [Hz]
νA 1521.18990
νB 1488.25620
νC 1447.58420
νD 1421.89690
5
JAB JHH n.r.*
4
JAC JHH 1.52410
3
JAD JHH 8.02600
3
JBC JHH 8.01740
4
JBD JHH 1.54630
3
JCD JHH 7.50070
HWB (global) 0.5039
5
Standard deviations better then 0.0006 Hz. *) JHH not resolved.
Remarks: Coupling constants listed above are consistent with spin assignment II and III. Chemical
1
shift predictions confirm assignment III. Compare the 200 MHz H NMR spectrum of 1-bromo-3-
chloro-benzene from Example 2 below.
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Four-Spin Systems
8.13.2 Example 2: ABCD System in m-C6H4BrCl – 1-Bromo-3-chloro-benzene
Br Br Br
H6 H2 HC HA HB HA
H5 Cl HD Cl HD Cl
H4 HB HC
Spin assignment
I II III
1
200 MHz H NMR Spectrum of 1-Bromo-3-chloro-benzene in CDCl3 + TMS
1500 1480 1460 1440 1420

(Hz)
1
Figure 314 : 200 MHz H NMR spectrum of 1-bromo-3-chloro-benzene in CDCl3 + TMS. Upper:
experimental. Lower: iterated.
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Four-Spin Systems
1
200 MHz H NMR Data for of 1-Bromo-3-chloro-benzene in CDCl3
Parameter Data [Hz]

νA 1501.82442
νB 1474.78032
νC 1453.67237
νD 1429.97668
4
JAB JHH 1.86405
4
JAC JHH 1.98668
5
JAD JHH 0.91439
4
JBC JHH 1.91502
3
JBD JHH 8.04712
3
JCD JHH 8.09334
HWB (global) 0.50390
Standard deviations are smaller than 0.0006 Hz
Remarks: Coupling constants listed above are consistent with spin assignment II and III. Chemical
1
shift predictions confirm assignment III. Compare the 200 MHz H NMR spectrum of 1-bromo-2-
chloro-benzene from Example 1 above. Memorize the spectral patterns of ortho- and meta
bromochlorobenzene.
8.13.3 Example 3: The 1H NMR Spectrum of 2-Sulfobenzoic Acid Ammonium

Salt
Another useful example is found in 2-sulfobenzoic acid ammonium salt, which, when dissolved in
D2O, dominantly exists in the form with a non-dissociated, deuterated COOD substituent. Dissolving
the 2-sulfobenzoic acid ammonium salt in NaOD/D2O leads to the fully deprotonated anion.
Corresponding 500 MHz spectra are shown in the subsequent sections.
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Four-Spin Systems
First and Second Deprotonation Products of 2-Sulfobenzoic Acid

COOD COO-
H SO3- H SO3-
H H H H
H H
in D2O in NaOD/D2O
The 500 MHz 1H NMR Spectrum of 2-Sulfobenzoic Acid Ammonium Salt in D2O
It is difficult to analyze this spectrum manually. Hence the automated analysis of TopSpin / DAISY is
welcome.
8.00 7.90 7.80 7.70 7.60

(ppm)
1
Figure 315 : 500 MHz H NMR spectrum of 2-sulfobenzoic acid ammonium salt dissolved in D2O.
Upper: experimental, lower: iterated.
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Four-Spin Systems
500 MHz 1H NMR Spectrum of 2-Sulfobenzoic Acid Ammonium Salt in NaOD/D2O
It is easier to analyze this ABCD spectrum manually.

Try your hand for start parameters and then simulate with TopSpin / DAISY:
1571.24
1570.24
1569.48
1563.77
1562.02
1518.79
1517.35
1511.39
1509.88
1504.23
1502.48
1501.54
1499.59
1493.82
1492.12
1486.35
1484.66
1474.56
1472.86
1467.91
1467.15
1465.52
7.95 7.90 7.85 7.80 7.75 7.70 7.65 7.60 7.55 7.50 7.45 7.40 7.35 7.30 7.25
(ppm
)
1
Figure 316 : 500 MHz H NMR spectrum of 2-sulfobenzoic acid ammonium salt dissolved in NaOD/D2O.
7.80 7.70 7.60 7.50 7.40 7.30

(ppm)
1
Figure 317 : 500 MHz H NMR spectrum of 2-sulfobenzoic acid ammonium salt dissolved in NaOD/D2O.
Upper: experimental, lower: iterated.
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Four-Spin Systems
1
Iterated 500 MHz H NMR Parameters of 2-Sulfobenzoic Acid Ammonium Salt
in D2O in D2O/NaOD
Parameter Hz Error Hz Error
ν1 A 1590.75602 0.00264 A 1566.50789 0.00198
ν2 B 1529.78148 0.00328 C 1494.03515 0.00170
ν3 C 1527.50117 0.00388 B 1509.36152 0.00178
ν4 D 1519.13486 0.00364 D 1470.52128 0.00197
J12 7.99444 0.00866 8.01694 0.00292
J13 1.19434 0.00834 1.21304 0.00229
J14 0.46262 0.00414 0.49864 0.00270
J23 7.53694 0.00716 7.47808 0.00424
J24 1.34273 0.00792 1.33584 0.00226
J34 7.71075 0.00551 7.65456 0.00312
HWB1 0.61998 0.00511 0.70093 0.00424
HWB2 0.57588 0.00561 0.70372 0.00339
HWB3 0.62195 0.00548 0.71950 0.00358
HWB4 0.62543 0.00445 0.70892 0.00224
Remember: Chemical shifts (resonance frequencies) in benzene derivatives are more sensitive to
3
substituent effects than coupling constants. Starting parameters can be set to: JHH(ortho) = 7-8 Hz.
4 5
JHH(meta) = 1-3 Hz. JHH(para) = 0-1 Hz. Guess the chemical shifts from the experimental spectrum
und start iterating TopSpin / DAISY. This approach should lead rapidly to convergence in iteration.
We will come back to benzene derivatives in chapters on 5- and 6-spin systems.
Results
in D2O in D2O/NaOD
Parameter Error Parameter Error
Baseline Offset 0.00693 0.00282 0.00332 0.00490
Baseline Ascent 0.00017 0.00005 0.00006 0.00006
Constants Defining Experimental Spectrum

D2O NaOD/D2O
First frequency point 1615.33116 1602.27270
Last frequency point 1491.01582 1437.44766
Number of points 3703 2628
Hz/Point 0.03358 0.06274
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Statistical Information
D2O NaOD/D2O
Final sum of squares 36.147752 54.595147
Number of spectral points 3703 2628
Degrees of freedom 3687 2612
Standard deviation of measurements 0.099016 0.144574
R-factor ( % ) 0.770706 0.384597
Connecting Spin Analysis with the Topological Analysis of Protons
Two spin assignments I and II for both anionic forms are consistent with coupling constants listed
above:
COOD COOD COO- COO-
H4 SO3- H1 SO3- H4 SO3- H1 SO3-
H3 H1 H2 H4 H3 H1 H2 H4
H2 H3 H2 H3
I II I II
Chemical shift prediction may be used to assign spins to specific proton positions. Since
dissociation COOD → COO is expected to have a stronger effect on chemical shift of H2 (para) than
-
for H3 (meta) assignment I seems the best solution for this situation.
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8.13.4 Example 4: 1H NMR Spectrum of Anthranilic Acid
ABCD with High First Order Character – Approaching the AMRX Case
Solutions in CD3OD from anthranilic acid or its corresponding anion give rise to ABCD spectra when
measured at 200 MHz.
COOD COO-
H4 ND2 H4 ND2
H3 H1 H3 H1
H2 H2
4% in CD3OD 4% in CD3OD + NaOD
7.90 7.80 7.70 7.60 7.50 7.40 7.30 7.20 7.10 7.00 6.90 6.80 6.70 6.60 6.50
(ppm)
1
Figure 318 : 200 MHz H NMR spectra of 4% anthranilic acid in CD3OD.
7.90 7.80 7.70 7.60 7.50 7.40 7.30 7.20 7.10 7.00 6.90 6.80 6.70 6.60 6.50
(ppm)
1
Figure 319 : 200 MHz H NMR spectra of 4% anthranilic acid in CD3OD + NaOD.
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Subsequent measurements at 500 MHz showed ABCD systems approximating the simpler AMRX
case:
7.8 7.6 7.4 7.2 7.0 6.8 6.6

1
Figure 320 : 500 MHz H NMR spectra of 4% anthranilic acid in CD3OD.
7.8 7.6 7.4 7.2 7.0 6.8 6.6

1
( )
Figure 321 : 500 MHz H NMR spectra of 4% anthranilic acid in CD3OD + NaOD.
Starting parameters for ABCD iterations are easily obtained following AMRX analysis.
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Results from iterations and spin assignment are given below:
1
500 MHz H NMR Spectra of Anthranilic Acid
4 % Anthranilic Acid 4 % Anthranilic Acid

in CD3OD in CD3OD + NaOD
Param Data Error Spin Data Error Spin
δ1 7.8122 A 7.7630 A
δ2 6.5714 D 6.7547 D
δ3 7.2260 B 7.2314 B
δ4 6.7315 C 6.8104 C
ν1 3906.11466 0.00035 A 3881.48761 0.00147 A

ν2 3285.71928 0.00033 D 3377.35200 0.00207 D
ν3 3613.00309 0.00032 B 3615.71684 0.00180 B
ν4 3365.76521 0.00039 C 3405.20341 0.00168 C
J12 8.05397 0.00046 7.85266 0.00226

J13 1.66292 0.00039 1.70740 0.00176
J14 0.45955 0.00045 0.29894 0.00675
J23 7.04932 0.00042 7.14645 0.00223
J24 1.15483 0.00040 1.22093 0.00208
J34 8.32759 0.00044 8.11185 0.00208
HWB1 0.70087 0.00072 1.05787 0.00428

HWB2 0.71152 0.00059 1.11128 0.00416
HWB3 0.69413 0.00040 0.96818 0.00333
HWB4 0.70090 0.00079 1.13527 0.00437
COOD COO-
H4 ND2 H4 ND2
H3 H1 H3 H1
H2 H2
Most Probable Spin Topology
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8.13.5 Some Further Examples for ABCD Systems
ABCD spectra occur quite frequently in aromatic patterns, in heterocycles like N-methyl-pyridone
and in olefinic structures like cis,trans-1,3-dichlorobutadiene.
Cl H
C C Cl
H C C
H H
In addition asymmetrically substituted cyclobutanes like
R1 R2
C C
H H
R1 H
C C
H R2
1
are characterized by ABCD H NMR spectra.
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8.14 The ABC2 and Related AB2C, A2BC Systems

Symmetrically meta-disubstituted benzenes C6H4R2 give rise to AB2C type spectra. Patterns are
largely influenced by substituent effects acting dominantly on chemical shifts and less on coupling
constants. It is useful to study the pair of dihalogenated compounds:
Br Cl
H H H H
H Br H Cl
H H
1
Comparing 200 MHz and 500 MHz H NMR Overview Spectra
of 1,3-Dibromobenzene and 1,3-Dichlorobenzene
MHz 200 500
m-C6H4Br2
7.50 7.40 7.30 7.20 7.10 7.00 6.90 7.50 7.40 7.30 7.20 7.10 7.00 6.90
(ppm) (ppm)
AB2C → AX Y 2 AB2C → AM X 2
m-C6H4Cl2
7.50 7.40 7.30 7.20 7.10 7.00 6.90 7.50 7.40 7.30 7.20 7.10 7.00 6.90
(ppm) (ppm)
AB2C AB2C → AX Y 2
1
Figure 322 : H NMR spectra of 1,3-dibromobenzene and 1,3-dichlorobenzene
1
To obtain starting parameters for iterations from those 500 MHz H NMR spectra do the familiar
sub-spectral analysis with approximations shown above and the following spectra:
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1
500 MHz H NMR Spectrum of m-C6H4Br2 and m-C6H4Cl2
7.50 7.40 7.30 7.20 7.10 7.00 6.90

(ppm)
1
Figure 323 : 500 MHz H NMR spectrum of m-C6H4Br2
7.28 7.24 7.20 7.16 7.12 7.08 7.04

(ppm)
1
Figure 324 : 500 MHz H NMR spectrum of m-C6H4Cl2
1
500 MHz H NMR Parameters [Hz] for m-C6H4Br2 and m-C6H4Cl2
Parameter m-C6H4Br2 m-C6H4Cl2

ν1 νA 3782.1500 3635.0000
ν2 νB2 3645.7500 3551.7500
ν3 νC 3457.7500 3525.4000
J12 JAB 1.8500 1.8500
J13 JAC 0.2900 0.2900
J23 JBC 8.0300 8.0300
HWB HWB 0.3000 0.3000
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Simulated Spectra - A Part

m-C6H4Br2 m-C6H4Cl2
1 3784.1578 0.9719 3637.0163 0.9533
2 3783.8658 0.9744 3636.6426 0.9608
3 3782.3222 0.9985 3635.2701 0.9938
4 3782.2951 0.9991 3635.1452 0.9974
5 3782.0283 1.0004 3634.8552 1.0026
6 3782.0051 1.0009 3634.8463 1.0023
7 3780.4593 1.0269 3633.3654 1.0415
8 3780.1674 1.0279 3633.0253 1.0476
Simulated Spectra – B2 Part

m-C6H4Br2 m-C6H4Cl2
9 3650.8516 1.9392 3557.9900 1.3604
10 3650.6826 1.9452 3556.3720 1.5849
11 3649.0159 1.8846 3556.2437 1.2483
12 3648.8197 1.8895 3554.4673 1.4845
13 3642.8269 2.1096 3549.6631 2.5029
14 3642.6551 2.1145 3548.9579 2.7239
15 3640.9661 2.0556 3547.8421 2.4249
16 3640.8175 2.0616 3547.1616 2.6648
Simulated Spectra – C Part

m-C6H4Br2 m-C6H4Cl2
17 3465.7506 1.0889 3532.2537 1.6862
18 3465.4585 1.0872 3531.8800 1.7050
19 3457.8949 1.0009 3525.5448 1.0026
20 3457.6049 0.9991 3525.2548 0.9974
21 3457.5541 0.9955 3523.2217 0.7814
22 3457.2601 0.9936 3522.7978 0.7576
23 3449.6984 0.9183 3516.5127 0.5447
24 3449.4065 0.9164 3516.1726 0.5275
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Identify those transitions in expanded spectra shown in the next figures:
1
Expanded 500 MHz H NMR Spectrum of m-C6H4Br2
3792 3788 3784 3780 3776 3772

(Hz)
Figure 325 : A part
3656 3652 3648 3644 3640 3636

(Hz)
Figure 326 : B2 part - approximates an M2 part
3464 3460 3456 3452 3448

(Hz)
Figure 327 : C part - approximates an X part
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1
Expanded 500 MHz H NMR Spectrum of m-C6H4Cl2
3644 3640 3636 3632 3628

(Hz)
Figure 328 : A part
3560 3556 3552 3548 3544

(Hz)
Figure 329 : B2 part - approximates a X2 part
3532 3528 3524 3520 3516

(Hz)
Figure 330 : C part - approximates a Y part
Remember AB2 and AB2X analysis. What do you extract from those two lines marked by red
arrows?
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8.14.1 Further Practical Examples
ABC2 to ABX2 Systems in Trans-CHCl=CH-CH2Cl
Parameter Type Data

H2
δ1 δH 6.315 ppm
Cl C Cl δ2 δH 6.053 ppm
δ3 δH 4.010 ppm
C C 3
J12 JHH 13.1 Hz
4
J13 JHH -1.1 Hz
H1 H3 H3
3
J23 JHH 7.2 Hz
1
H NMR Data for Trans-CHCl=CH-CH2Cl. δH vs. int. TMS. Solvent: CCl4.
1
H NMR spectra of trans-CHCl=CH-CH2Cl at lower spectrometer frequencies show strongly coupled
ABC2 patterns. 200 MHz and 500 MHz spectra appear simpler, approximating ABX2 cases.
6.4 6.0 5.6 5.2 4.8 4.4 4.0

(ppm)
1
Figure 331 : 200 MHz H NMR spectrum of trans-CHCl=CH-CH2Cl. total spectrum.
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This ABC2 case approximates the ABX2 situation as visible in expanded spectra below:
Expanded Spectra
6.30 6.20 6.10 6.00

(ppm)
1
Figure 332 : 200 MHz H NMR spectrum of trans-CHCl=CH-CH2Cl. AB part.
840 830 820 810 800 790 780 770

(Hz)
1
Figure 333 : 200 MHz H NMR spectrum of trans-CHCl=CH-CH2Cl. C2 part (close to X2).
For details see: E. W. Garbisch Jr.; J. Chem. Ed. 45, 480-493 (1968).
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8.15 The [AB]2 System Part 1: o-Disubstituted Benzenes

JAA´
1 4 A A´
JAB JAB´
2 3 B B´
JBB´
Practical chemistry delivered a broad variety of organic and inorganic compounds which give rise to
[AB]2 spectra.
H R1
H H
H R H H
R1 C C R2
H R H H
H H
2
H R
H H R1
H 1 H H H
O R C O :
O C C O S
H R2 H O R2
H H H H
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R1 R1 R1 R2 R1 R2
H H H H H H
R2 R2 R2 R1 R1 R2
H H H H H H
Cl H H H H Cl
H Cl H
H Cl H
H Cl H H Cl H
Corresponding spin systems have an element of two-fold symmetry and are characterized by the
following conditions:
[1] ν A =ν A´
[2] νB =νB´
[3] JAB = JA´B´
[4] JAB´ = JA´B
where
[5] JAB ≠ JAB´
If
[6] JAB = JAB´

then the spin symmetry is higher and the system is described by A2B2, See chapter 8.20.
A typical [AB]2 spectrum has up to 28 lines, as 14 pairs symmetrically arranged around the central
midpoint frequency νC in
ν + νB
[7] ν C = A
2
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4 of those 28 lines are usually very weak, henceforth in practice 24 lines will be seen in a standard
[AB]2 spectrum.
In order to simplify practical [AB]2 analysis it is convenient to center (shift) the total spectrum around
zero defining:
[8] ν C =0
[9] ν A = − νB
[10] ν A > νB
Then the analytical approximations of DISCHLER and ENGLERT, if necessary in combination with
SPIRKO's or NAGESWARA-RAO and VENKATESWARLU´s methods, may be used to obtain
conveniently explicit expressions for most of the transition frequencies and intensities in [AB]2
spectra.
Let us start here with the DISCHLER - ENGLERT approach.
The A part is the left (low field) half spectrum showing twelve lines enumerated from left to right by
Latin letters:
a b c d e f g h i j k l (and two weak lines: m n)
The B part is the right (high field) half spectrum, a mirror image of the A part). Corresponding lines
are enumerated from right to left with:
a´ b´ c´ d´ e´ f´ g´ h´ i´ j´ k´ l´ (and two weak lines: m´ n´)
In general the four weak lines m, n, m´, and n´ are not observed experimentally.
To extract the resonance frequencies νA or νB resp. and the four coupling constants JAB, JAB´, JAA´,
and JBB´ it suffices to inspect one half spectrum only.
For [AB]2 analysis four auxiliary parameters, linear combinations of coupling constants, are used:
[11] =
N JAB + JAB´
[12] =
L JAB − JAB´
[13] =
K JAA´ + JBB´
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[14] =
M JAA´ − JBB´
and additional parameters:
ν A + νB
[15]=
νC = 0
2
[16] ∆ ν = ν A − νB = 2 ν A
[17] C = ∆ 2ν + N2
[18] D = ( ∆ ν + M)2 + L2
[19] F = ( ∆ ν − M)2 + L2
[20] =
G M2 + L2
Parameters N, L, K and M Determine Characteristic Patterns of [AB]2 Spectra
For practical reasons the multitude of proton [AB]2 spectra were divided into four typical patterns
(classes) which are determined by specific relations of corresponding N, L, K und M parameters.
This is shown in the following table:
Class Condition Type of Compound Example

H
Symmetrically
H Cl
1,2-disubstituted
1 N>K>L>M benzene derivatives
H Cl
ortho-benzene derivatives
H
Br
Asymmetrically
H H
1,4-disubstituted
2 N ≈ L > K >> M benzene derivatives
H H
para-benzene derivatives
Cl
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Class Condition Type of Compound Example

H H
Asymmetrically
3 K > N >> L > M 1,2-disubstituted Cl C C Br
1,2-ethane derivatives
H H
H
Symmetrical cyclic structures H
with ethane fragments C O
4 K ≈ L >> M ≈ N dioxolane, ethylenesulphite, C O
phospholane, and similar H C R1
H
R2
In the forthcoming chapters we will inspect those four typical spectral types and learn about pattern
recognition and similarity of spectra. In addition we will learn that substituent effects and steric strain
will influence significantly the relations between parameters N, L, K and M and hence the spectral
patterns.
For introduction to [AB]2 spectral analysis an example of class 1 is chosen:
HB HB
HA HX 1 HA
H{1H}-Decoupling
Fe(CO)3 Fe(CO)3
HA´ HX´ HA´
HB´ HB´
This benzocyclobutadiene complex gives rise to a total [ABX]2 system which by decoupling the X-
1 1
nuclei in H{ H } NMR yields the [AB]2 spectrum wanted.
For details read:
H. Günther, Angew. Chem. 84, 907 (1972); Angew. Chem. Int. Ed. Engl. 11, 861 (1972).
1 1
The HX-decoupled H{ H} NMR spectrum exhibits a didactically useful [AB]2 system of aromatic
protons in an ortho-benzene structure. This spectrum is particularly suitable, since all 12 lines (a to
l) are neatly separated and visible at 100 MHz. Increasing the field reduces the number of separable
lines: 200 MHz: 11 lines; 400 MHz: 10 line; and 800 MHz: 10 lines, where [AB]2 approximates [AX]2.
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Compare Simulated 100, 200, 400 and 800 MHz Spectra Shown in ppm Scale
0.20 0.10 -0.00 -0.10 -0.20
Figure 334 : 100 MHz spectrum
0.20 0.10 -0.00 -0.10 -0.20
0.20 0.10 -0.00 -0.10 -0.20
0.20 0.10 -0.00 -0.10 -0.20
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Compare Simulated 100, 200, 400 and 800 MHz Half Spectra Shown in Hz Scale
14 10 6 2
(Hz)
24 20 16 12 8 4
(Hz)
36 32 28 24 20 1
(Hz)
64 60 56 52 48 44
(Hz)
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For didactical reasons the 100 MHz spectrum will be studied in details in the following section.
0.9
0.8
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0
25 20 15 10 5 0 -5 -10 -15 -20 -25
[Hz]
Figure 342 : 100 MHz H NMR spectrum with resonance frequencies centered around νC = 0
1
NMR Parameters Used for Simulation

ν1=ν4 6.75 νA 6.75
ν2=ν3 -6.75 νB -6.75

3
J12 = J34 8.61 JHH(ortho) JAB 8.61
4
J13 = J24 0.69 JHH(meta) JAB´ 0.69
3
J14 6.78 JHH(ortho) JAA´ 6.78
5
J23 1.57 JHH(para) JBB´ 1.57
νC 0 (νA + νB)/2 0
∆ν 13.50 νA - νB 13.50
N 9.30´ JAB + JAB´ 9.30´
L 7.92 JAB - JAB´ 7.92
K 8.35 JAA´ + JBB´ 8.35
M 5.21 JAA´ - JBB´ 5.21
4 5
Note: JHH(meta) < JHH(para). See discussion below.
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Numerical Spin Assignment Used for Simulations:

2
1
Fe(CO)3
4
3
Simulated Transition Frequencies and Intensities and Dischler-Englert Assignment
DE Line Frequency Intensity DE Line Frequency Intensity

Assign No. [Hz] [rel.] Assign No. [Hz] [rel.]
g 1 16.7945 0.098 13 j -0.4012 0.944
c 2 14.8996 0.168 14 f´ -0.9926 1.180
k 3 13.1678 0.778 15 l´ -3.053 3.688
a 4 12.8466 0.865 16 b´ -3.5466 3.135
d 5 10.4726 0.820 17 e´ -5.4186 1.832
h 6 9.2594 1.140 18 i´ -7.1339 1.349
i 7 7.1339 1.349 19 h´ -9.2594 1.140
e 8 5.4186 1.832 20 d´ -10.4726 0.820
b 9 3.5466 3.135 21 a´ -12.8466 0.865
l 10 3.0529 3.688 22 k´ -13.1678 0.778
f 11 0.9926 1.180 23 c´ -14.8986 0.168
j´ 12 0.4012 0.944 24 g´ -16.7945 0.098
Note the overlap of half spectra: frequency of line j´ > frequency of line j
The twelve lines of a half spectrum are divided into four characteristic groups,
Group Lines
1 a b
2 c d e f
3 g h i j
4 k l
which will be dealt with in separate subsections as shown below.
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Group 1. N-lines a and b
N C
b b’
a a’
νC1
Figure 343 : Group 1. N-lines a and b
Two lines a and b (A part) form the left half of a characteristic sub-spectrum. Frequencies are given
by:
C +N
[21] a =
2
C −N
[22] b =
2
corresponding intensities by:
C −N
[23] Ia = 2 ⋅
C
C+N
[24] Ib = 2 ⋅
C
[25] Ia : Ib = b : a
[26] Ia + Ib =
4
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Lines a and b are centered at νC1:
a+b C
[27] ν C1
= =
2 2
Lines a´ and b´ (B part) form the high field half of this ab- type sub-spectrum.
By direct analysis parameters N, C, ∆ν, and νA are obtained:
[28] N= a − b
[29] C= a + b
[30] ∆ ν =2 ab
∆ν
[31] ν A = − νB =
2
Numerical Evaluation of Example:
DE Line Frequency Intensity

Assign No. [Hz] [rel.]
a 4 12.8466 0.865
b 9 3.5466 3.135
Eqs. Results Eqs. Results
[28] N= a − b 9.30 Hz [29] C= a + b 16.39 Hz
∆ν
[30] ∆ ν =2 ab 13.50 Hz [31] ν A = − νB = 6.75 Hz
2
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Group 2. M, L-lines: c d e f
D-F G
f
d
νC2
Figure 344 : Group 2. M, L-lines: c d e f
Four lines c d e f form a “distorted“ ab type sub-spectrum, which is centered around νC2:
D +F
[32] =
ν C2 =
2
Frequencies for those four lines are defined by:
D+G
[33] c =
2
F+G
[34] d =
2
D−G
[35] e =
2
F−G
[36] f =
2
and corresponding intensities by:
M ⋅ (∆ ν +M) L2
[37] Ic =1− −
G ⋅D G ⋅D
M ⋅ (∆ ν -M) L2
=
[38] Id 1+ −
G ⋅F G ⋅F
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M ⋅ (∆ ν +M) L2
[39] Ie = 1+ +
G ⋅D G ⋅D
M ⋅ (∆ ν -M) L2
[40] If =
1− +
G ⋅F G ⋅F
Sums of intensities follow rules:
[41] Ic + Ie = Id + If = 2
[42] Ic + Id + Ie + If =4
Analytical expressions for parameters ∆ν, M, G, and L are given with:
[43] =
∆ν 2(c e + df )
c e − df
[44] M =
∆ν
[45] G = c − e = d − f
[46]=L G2 − M2
The auxiliary parameters D and F are found by:
[47] D= c + e
[48] F= d + f
Numerical Evaluation of Example:

c 2 14.8996 0.168
d 5 10.4726 0.820
e 8 5.4186 1.832
f 11 0.9926 1.180
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[43] =
∆ν 2(c e + df) 13.5000 Hz [47] D= c + e 20.3172 Hz
[48] F= d + f 11.4652 Hz [45] G = c − e = d − f 9.4800 Hz
c e −df
[44] M = [46]=L G2 − M2
∆ν 5.2100 Hz 7.9200 Hz
Group 3. K, L Lines g h i j
½ K-E2-E3 E2-E3
i
h
j
νC3
Figure 345 : Group 3. K, L lines g h i j
Those four lines form another "distorted“ ab type sub-spectrum, centered around νC3 which is
identical with νC1 found by inspection of the a and b N-lines.
C
[49] ν C3 =
ν C1 =
2
The four frequencies g h i j are defined by equations:
C K
[50] g = + − E3
2 4
C K
[51] h = − + E2
2 4
C K
[52] i = + − E2
2 4
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C K
[53] j = − + E3
2 4
Parameter C follows from:
[54] C = g + j = h + i
No explicit algebraic formula can be given, neither for terms E2 and E3 nor for intensities of lines
g h i j.
Group 4. Lines k and l
Figure 346 : Group 4. Lines k and l and corresponding l´ and k´
Lines k and l are found at:
C K
[55] k =
− + − E4
2 4
C K
[56] l =
− − + E1
2 4
Again no explicit algebraic formula can be given, neither for terms E1 and E4 nor for intensities
of lines k and l.
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E1 to E4 are Eigenvalues of the secular equations. But the following relations hold:
[57] E1 + E2 + E3 + E4 =
−N (E1 ≥ E2 ≥ E3 ≥ E4 )
[58] Ig + Ih + Ii + Ij + Ik + Il = 8 − ε
where ε corresponds to the sum of intensities for the two weak lines m and n:
[59] ε= Im + In
a value, which will be close to zero.

The combination of parameters for the [AB]2 system will influence the distribution of relative
intensities:
[60] Ig + Ih + Ii + Ij >< 4
[61] Ik + Il <> 4
which will be discussed later.
Finally the parameter K is found from lines g h i j k l :

Using equations [50] to [53] and [55] to [57] E1 to E4 are eliminated leading to:
[62] (g − h) + (k − l) = K + N
[63] K = (g − h) + (k − l) − (a − b)
In practice it is useful to define a "correction term” T:
[64] T = (k − l) − (a − b)
leading to a simplified expression for K:
[65] K = (g − h) + T
We will find that T approximates zero if [AB]2 transforms into [AX]2 e. g. by increasing the field
strength B0. Hence in simple cases the difference (g - h) yields a reasonable value for K, which may
be used to start subsequent iterations.
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Numerical Evaluation of Examples:

g 1 16.7945 0.098
k 3 13.1678 0.778
h 6 9.2594 1.140
i 7 7.1339 1.349
l 10 3.0529 3.688
j 12 -0.4012 0.944

[63] K = (g − h) + (k − l) − (a − b) 8.3500 Hz [54] C = g + j = h + i 16.3933
Remarks: It is interesting to check the correction term T from eq. [64] for an approximation of K.
T = (k – l) – (a – b) = 0.8149 Hz. The difference (g - h) = 7.5351 approximates the parameter K well
enough to start iterations. If not, then use eq. [63] for a correct solution in K.
Remark: Many publications dealt with the Dischler-Englert method of analyzing [AB]2 type spectra.
For details read:
a) B. Dischler and W. Maier, Z. Naturforschg. 16A, 318-319 (1961);
b) B. Dischler and G. Englert, Z. Naturforschg. 16A, 1180-1190 (1961);
c) B. Dischler, Z. Naturforschg. 20A, 888-901 (1961); B. Dischler, Angew. Chem. 78, 653-663
(1966).
d) An overview dealing with the analysis of [AX]2 and [AB]2 type spectra was presented by H.
Günther, Angew. Chem. 84, 907-920 (1972).
SPIRKO's Solution for K2 and the Sign of K
Ordering the spectral lines according to DISCHLER and ENGLERT is not trivial. In many cases the
sequence g h i j does not simply follow from left to right in the spectrum. Pairs (g j) and (h i),
and the same is true for (k l), may interchange leaving a total of 8 permutations. SPIRKO solved
this problem by introducing auxiliary variables as shown in the following expressions:
C
[66] g= g −
2
C
[67] h= h −
2
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C
[68] i = i−
2
C
[69] j = j−
2
C
[70] k= k +
2
C
[71] l = l+
2
to obtain the square of K:
g2 + h 2 + i 2 + j 2 + 2( k 2 + l 2 ) − 4 ∆ 2ν − 3(N2 + L2 )
[72] K 2 =
2
The sign of K relative to N is determined by two NMR experiments at two different magnetic
fields B0(1) and B0(2). Comparing the eight possible permutations for lines in:
[73] Q = (g − j) + (h − i) + 2(k − l)
only two combinations are invariant for experiments in both magnetic fields, exactly if:
[74] Q =
± 2(N + K)
which leads directly to the sign of K.
For details read: V. Spirko, Coll. Czech. Chem. Comm, 35, 980-984 (1969).
Another problem occurs for systems where |K| » |N|. Very often in practical spectra the outer lines of
the g h i j part are weak and invisible leaving only the inner pair for analysis of K.
In such situations the approximation of NAGESWARA-RAO and VENKATESWARLU may be
applied.
Using
(h − i) K
[75] X=
2 = E2 −
2 4
leads to:
3 2
N - ∆ ν2 )
L2 (3 x 2 -
[76] K= 3 4
4 x + 4N x - x (N2 + 4 ∆ 2ν )- N3
2
where
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[77] x = X2
An analogous expression holds for
[78] x = X3
if
( j − g) K
[79] X=
3 = E3 −
2 4
For details read:

B. D. Nageswara-Rao and P. Venkateswarlu, Proc. Indian Acad. Sci. 54A, 1-12 (1961).
Some Comments on the Signs of Parameters N, L, K, und M
1. Signs of L and M do not affect the spectral pattern of an [AB]2 spectrum.
2. Changing the sign of one parameter, either N or K, affects the frequencies and the intensities
of the g h i j k l lines, but not those of the c d e f lines.
3. In addition the assignment of N-lines a and b is reversed if the sign of N is changed.
4. Changing the sign of K reverses the order of lines g h i j .
5. The appearance of an [AB]2 spectrum is strongly influenced by the sign of K/N.
6. We will recognize two different patterns for combinations of N and K having identical or non-
identical signs in N and K.
7. By comparison of experimental and calculated spectra the relative signs of N and K may be
found, but not those of M and L.
8. Since the total spectrum is invariant for multiplication of ALL coupling constants with (-1) the
experimental spectrum does not yield absolute signs.
9. Two parameter combinations (Type 1 and Type 2) leading to [AB]2 spectra are listed in the
following table:
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Type 1 Type 2
[AB]2 Case ++++ [AB]2 Case ++--
Parameters [Hz] [Hz]
νA + 6.75 + 6.75
νB - 6.75 - 6.75
JAB + 8.61 + 8.61

JAB + 0.69 + 0.69
JAA´ + 6.78 - 6.78
JBB´ + 1.57 - 1.57
N + 9.30 + 9.30
L + 7.92 + 7.92
K + 8.35 - 8.35
M + 5.21 - 5.21
Lines Frequency Intensity Frequency Intensity

a + 12.847 (0.865) + 12.847 (0.865)
b + 3.547 (3.135) + 3.547 (3.135)
c + 14.900 (0.865) + 14.900 (0.865)

d + 10.473 (0.865) + 10.473 (0.865)
e + 5.419 (1.832) + 5.419 (1.832)
f + 0.993 (1.180) + 0.993 (1.180)
g + 16.795 (0.098) - 0.577 (2.735)

h + 9.259 (1.140) + 5.771 (1.763)
i + 7.134 (1.349) + 10.622 (0.840)
j - 0.401 (0.944) + 16.970 (0.098)
k + 13.168 (0.778) + 12.014 (0.997)

l + 3.053 (3.688) + 4.716 (1.559)
The simulated spectrum of Type 1 corresponds to the spectrum shown and discussed above. The
spectrum of Type 2 is shown in a subsequent section.
If we look deeper into this [AB]2 problem a total of 8 permutations may be derived, where 4
permutations form Type 1 or Type 2 spectra as shown in the following Table:
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Identical [AB]2 Systems:
Parameter Type 1 ++++ Type 2 ----

1 2 3 4 5 6 7 8
JAB +8.61 +8.61 +0.69 +0.69 +8.61 +8.61 +0.69 +0.69
JAB´ +0.69 +0.69 +8.61 +8.61 +0.69 +0.69 +8.61 +8.61
JAA´ +6.78 +1.57 +6.78 +1.57 -6.78 -1.57 -6.78 -1.57
JBB´ +1.57 +6.78 +1.57 +6.78 -1.57 -6.78 -1.57 -6.78
N +9.30 +9.30 +9.30 +9.30 +9.30 +9.30 +9.30 +9.30

L +7.92 +7.92 -7.92 -7.92 +7.92 +7.92 -7.92 -7.92
K +8.35 +8.35 +8.35 +8.35 -8.35 -8.35 -8.35 -8.35
M +5.21 -5.21 +5.21 +5.21 -5.21 +5.21 -5.21 +5.21
Resonance frequencies for all those 8 combinations are given by:
νA 6.75 Hz νB -6.75 Hz
10. Further eight permutations are valid having reversed signs for all coupling constants.
Conclusion: Conventional spectral analysis of [AB]2 spectra in general does not lead to a unique
solution for coupling constants. But this problem is overcome in practice by using compound-specific
3 4 5
signs of coupling constants, e. g. signs for JHH(ortho), JHH(meta), and JHH(para) in benzene
2 3
derivatives are positive. JHH is negative while JHH is positive for ethane structures, etc..
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Type 2. [AB]2 Case ++-- and Decomposition Following the Dischler-Englert Method
25 20 15 10 5 0 -5 -10 -15 -20 -25

[Hz]
Figure 347 : Type 2. Total spectrum of [AB]2 case ++--.
b b’
a a’
N C
νC1
Figure 348 : Type 2. a b lines from [AB]2 case ++--.
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D-F G
νC2
Figure 349 : Type 2. c d e f lines from [AB]2 case ++--.
½K-E2-E3 E2-E3
νC3
Figure 350 : Type 2. g h i j lines from [AB]2 case ++--.
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½K-E1-E4 E1-E4-C
l l’
k k’
Figure 351 : Type 2. k l l´ k´ lines from [AB]2 case ++--.
NMR Parameters Used to Simulate the Spectrum of Type 2

ν1 = ν 2 νA = νA´ 6.75
ν3 = ν 4 νB = νB´ -6.75
J12 = J34 JAB = JA´B´ 8.61
J13 = J24 JAB´ = JA´B 0.69
J14 JAA´ -6.78
J23 JBB -1.57
N 9.30
L 7.92
K -8.35
M -5.21
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Transition Frequencies and Intensities for the Spectrum of Type 2

[Hz] [rel.] [Hz] [rel.]
1 16.970 0.098 13 -0.577 2.735
2 14.900 0.168 14 -0.993 1.180
3 12.847 0.865 15 -3.547 3.135
4 12.014 0.997 16 -4.716 1.559
5 10.622 0.840 17 -5.419 1.832
6 10.473 0.820 18 -5.771 1.763
7 5.771 1.763 19 -10.473 0.820
8 5.419 1.832 20 -10.622 0.840
9 4.716 1.559 21 -12.014 0.997
10 3.547 3.135 22 -12.847 0.865
11 0.993 1.180 23 -14.900 0.168
12 0.577 2.735 24 -16.970 0.098
Further Exercises for [AB]2 Analysis:
1 N > K > L >M Symmetrically disubstituted ortho-benzene derivatives
8.15.1 Example 1: Centered 1H NMR Spectrum of o-Dibromobenzene
b l
d,h
e
i
k
a
f,j
g c
0 20.0 10.0 0.0 -10.0 -20.0

1
Figure 352 : Centered 200 MHz H NMR spectrum of o-dibromobenzene
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1
Dischler-Englert Analysis of the 200 MHz H NMR Spectrum
N - lines [Hz]
a 18.720
b 9.070
∆ν 26.061
νC1 13.895
N 9.650
C 27.790
M,L - lines
c 21.870
d 14.860
e 12.110
f 5.160
∆ν 26.135
νC2 13.500
M 7.200
G 9.730
L 6.545
(g h I j) - lines
g 22.620
h 14.860
i 12.910
j 5.160
νC3 13.887
(k l) - lines
k 18.350
l 8.620
T 0.080
K 7.840
1
NMR Parameters for Centered 200 MHz H NMR Spectrum of o-Dibromobenzene
H1
H2 Br
H3 Br
H4
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Parameters Parameters Parameters Data [Hz]

ν1 = ν 4 νA = ν A 13.068
ν2 = ν 3 νB = ν B -13.068
∆ν ∆ν 26.136
νC νC 0
3
J12 = J34 JAB = JA´B´ JHH(ortho) 8.097
4
J13 = J24 JA´B = JAB´ JHH(meta) 1.553
5
J14 JAA´ JHH(para) 0.320
3
J23 JBB´ JHH(ortho) 7.520
N N 9.650
L L 6.544
K K 7.840
M M 7.200
8.15.2 Example 2: A Non-Centered 1H NMR Spectrum of o-Dichlorobenzene
In the early years of NMR o-Dichlorobenzene was used as test sample for resolution und
1
homogeneity of the magnetic field. Corresponding parameters for a 200 MHz H NMR spectrum are
given below (solution in CDCl3). Compare the results from ortho-dichloro- and ortho-dibromo-
benzene shown above.
NMR Parameters for o-Dichlorobenzene (in CDCl3; 200 MHz Analysis)

Parameter Parameter Data [Hz]
ν2 = ν 3 νA = ν A 1508.0300
ν1 = ν 4 νB = ν B 1465.7970
∆ν ∆ν 42.3550
νC νC 1486.9135
3
J12 = J34 JAB = JA´B´ JHH (ortho) 8.1025
4
J13 = J24 JA´B = JAB´ JHH (meta) 1.4947
3
J14 JBB´ JHH (para) 0.2131
3
J23 JAA´ JHH (ortho) 7.5946
N N 9.5972
L L 6.6078
K K 7.8077
M M 7.3815
HWB HWB global 0.3
N > K > M > L
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8.15.3 Example 3: Substituent Effects in o-Disubstituted Benzene

Derivatives
Coupling constants are less sensitive to substituent effects having narrow expectation ranges:
3 4 5
JHH(ortho) ca. 8 Hz. JHH(meta) ca. 1.5 Hz. JHH(para) ca. 0.3 Hz. Chemical shifts are more
sensitive.
S. Castellano and R. Costellnik (Tetrahedron Letters 51, 5211-5216 (1967)) studied symmetrically
o-disubstituted benzenes o-C6H4R2 (R = Cl, Br, I, tBu: 10% in CCl4. R = NO2: 10% in CH3COCH3)
and found the following data:
Ortho-disubstituted Benzenes
H A
H R B
H R B´
H A´
NMR Data of o-C6H4R2 (R = Cl, Br, I, tBu: 10% in CCl4. R = NO2: 10% in CH3COCH3)
Parameter o-C6H4Cl2 o-C6H4Br2 I NO2 tBu
δA 7.3655 7.5437 7.8091 8.1576 6.9725 [ppm]
δB 7.1097 7.0791 6.9589 8.0058 7.4466 [ppm]
JAB = JA´B´ 8.040 7.972 8.021 8.123 8.105 [Hz]
JA´B = JAB´ 1.537 1.504 1.488 1.488 1.591 [Hz]
JAA´ 0.315 0.302 0.299 0.299 0.273 [Hz]
JBB´ 7.449 7.467 7.314 7.314 7.002 [Hz]
N 9.577 9.478 9.509 9.611 9.696 [Hz]
L 6.503 6.468 6.533 6.35 6.514 [Hz]
K 7.764 7.769 7.613 7.613 7.275 [Hz]
M -7.134 -7.1965 -7.015 -7.015 -6.729 [Hz]
All examples obey: N > K > M > L
More information on NMR parameters of ortho-, meta-, and para-disubstituted benzenes is given by:
R. W. Crecely, J. M. Read, Jr., R. S. Butler, J. R. Goldstein; Spectrochim. Acta 24A, 685-694
(1968).
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8.15.4 Example 4: Steric Strain and NMR Parameters
Steric strain in benzocycloalkene derivates influences significantly the NMR parameters of the
aromatic ring system.
Benzocycloalkenes
H1 H1 H1
H2 H2 H2 CH2
CH2
CH2 CH2
CH2
H3 H3 H3 CH2
H4 H4 H4
δ1=δ4 7.1492 6.9069 7.0730
δ2=δ3 7.1891 6.7639 6.9900

J12=J34 6.04 7.36 7.59
J13=J24 0.33 1.00 1.17
J14 1.85 1.03 0.48
J23 7.63 7.79 7.20
N 6.37 8.36 8.76
L 5.71 6.36 5.42
K 9.48 8.82 7.68
M 5.78 6.76 6.72
K > N > M ≈ L K > N > M > L N > K > M > L
J12=J34 < J23 J12=J34 < J23 J12=J34 > J23
3 3 3 3 3 3
JHH < JHH JHH < JHH JHH > JHH
J13=J24 < J14 J13=J24 ≅ J14 J13=J24 > J14
4 5 4 5
JHH ≅ JHH
4 5
JHH < JHH JHH > JHH
δ [ppm]. J [Hz].
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Benzocycloalkenediones
H1 H1 O H1 O
H2 O H2 C H2 C
C CH2
CH2
C CH2
H3 O H3 C H3 C
H4 H4 O H4 O
δ1 8.0802 7.9629 8.0453
δ2 7.8556 7.8450 7.7731

J12=J34 7.71 7.73 7.81
J13=J24 0.77 1.05 1.30
J14 1.23 0.83 0.58
J23 7.15 7.34 7.34
N 8.48 8.78 9.11
L 6.94 6.68 6.51
K 8.38 8.17 7.92
M 5.92 6.51 6.76
N ≈ K > L > M N > K > L ≈ M N > K > M ≈ L
J12=J34 > J23 J12=J34 > J23 J12=J34 > J23
3 3 3 3 3 3
JHH > JHH JHH > JHH JHH > JHH
J13=J24 < J14 J13=J24 > J14 J13=J24 > J14
4 5 4 5 4 5
JHH < JHH JHH > JHH JHH > JHH
δ [ppm]. J [Hz].
Pay attention to the assignment of chemical shifts and the coupling constants.
For details read: M. A. Cooper, S. Mannatt; J. Amer. Chem. Soc. 92, 1605-1614 (1970).
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8.15.5 Example 5: 7,7-Difluoro-benzo-cyclo-propene
1
100 MHz H NMR Spectrum [AB]2X2 Spin System
1 19
100 MHz H{ F} NMR Spectrum [AB]2 Spin System
H1
H2 C
F5
C C
C C
F6
H3 C
H4
100 MHz NMR Parameters for 7,7-Difluoro-benzo-cyclo-propene.

Solution in CCl4. Ref. int. TMS. Ref. ext. CFCl3. Iterated with LAOCOON III.
Parameter Type Data

δA δ1 = δ4 δH 7.6062 [ppm]
δB δ2 = δ3 δH 7.4834 [ppm]
δx δ5 = δ6 δF -80.4 [ppm]
N 8.20 [Hz]
L 6.52 [Hz]
K 9.34 [Hz]
M 5.56 [Hz]
3
JAB = JA´B´ J12 = J34 JHH (ortho) 6.86 [Hz]
3
JAB´ = JA´B J13 = J24 JHH (meta) 0.34 [Hz]
3
JAA´ J23 JHH (ortho) 7.45 [Hz]
5
JBB´ J14 JHH (para) 1.89 [Hz]
4
JBX = JBX´ J15 = J16 = J45 = J46 JFH 3.64 [Hz]
5
JAX = JAX´ J25 = J26 = J35 = J36 JFH -0.33 [Hz]
K > N > L > M
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1
The 100 MHz H NMR spectrum represents an [AB]2X2-spin system.
770 765 760 755 750 745 740 735

(Hz)
1
Figure 353 : 100 MHz H NMR spectrum. [AB]2X2-spin system.
Decoupling the fluorine spins reduces the complexity of 6-spins case to a simpler 4-spin case
leading to the residual [AB]2 spin system.
770 765 760 755 750 745 740 735

(Hz)
19 1 19
Figure 354 : F decoupled 100 MHz H{ F} NMR spectrum. [AB]2 spin system.
Remember the reverse order of magnitude in this sterically strained molecule:

3 5
JHH(meta) = 0.34 Hz and JHH(para) = 1.89 Hz. This phenomenon was also observed for the parent
benzocyclopropene mentioned above.
For details read: H. Günther, J. B. Pawliczek; Org. Magn. Res. 3, 267-278 (1971).
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8.15.6 Example 6: A 1H{31P} NMR Spectrum of o-Phenylene Phosphorochlorodite
1 31
The centered 100 MHz H{ P} NMR spectrum of o-phenylene phosphorochlorodite, a benzo-1,3-
dioxa-2-phospholene derivative (30 mol % in CDCl3), can be described with the following
parameters:
H1
H2 O
P Cl
H3 O
H4
Parameter Data [Hz]

ν2 = ν 3 νA 6.420
ν1 = ν 4 νB -6.420
J12 = J34 JAB = JA´B´ 8.046
J13 = J24 JA´B = JAB´ 1.277
J23 JAA´ 7.692
J14 JBB´ 0.454
N 9.323
L 6.769
K 8.146
M 7.431
N > K > M > L
Exercise: Simulate the spectrum.
8.15.7 Example 7: ortho-Polyphenylenes
Cyclic polyphenylenes [C6H4]n gave rise to stereo chemical studies supported by NMR
spectroscopy. A interesting report “Proton Magnetic Resonance Spectra of the Atropisomers of
ortho-Hexaphenylene” was given by L. Ernst, A. Mannschreck, K. D. Rümpfer, Org. Magn. Res. 5,
125-128 (1973. This paper also includes ortho-Tetraphenylene and deals with [AB]2 and ABCD
systems.
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8.15.7.1 Example 7a: [AB]2 in ortho-Tetraphenylene
Parameter Set 1 Set 2

ν1 711.92 νA 699.43 νB
ν2 699.43 νB 711.92 νA
3
J12 JHH (ortho)´ 7.64 JAB 7.64 JAB
4
J12´ JHH (meta) 1.35 JAB´ 1.35 JAB´
3
J22´ JHH (ortho) 7.47 JAA´ 7.47 JBB´
5
J11´ JHH (para) 0.55 JBB´ 0.55 JAA´
N 8.99 8.99
L 6.29 6.29
K 8.02 8.02
M 6.92 -6.92
N > K > M > L
[AB]2 analysis (like AB analysis) yields the absolute value of ∆ν(AB) = νA-νB but is not able to assign
resonance frequencies specifically. Hence two different sets of NMR parameters result differing in
the assignment of resonance frequencies for A- and B-spins. By analogy to known compounds set 1
above is more likely than set 2. In the majority of ortho-disubstituted benzene derivatives 1,2-
C6H4R2 protons ortho to substituents R resonate to higher frequencies than meta-protons.
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Simulations using the data given above yield the following spectrum:
720 715 710 705 700 695 690

(Hz)
1
Figure 355 : Simulated 100 MHz H NMR. 3 mol % in CS2. Ref. int. TMS. HWB = 0.16 Hz.
5
Since the global HWB is as low as 0.16 Hz inter-ring couplings of type JHH between B-nuclei seem
unlikely.
8.15.7.2 Example 7b: [AB]2 in ortho-Hexaphenylene - Atropisomer 1
Ortho-Hexaphenylene exists in two distinct atropisomeric forms. The molecular geometry of the high
symmetric atropisomer 1 is shown below:
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Corresponding data are listed

ν1 704.00 νA 694.75 νB
ν2 694.75 νB 704.00 νA
3
4
3
J22´ JHH (ortho) 7.40 JBB´ 7.40 JAA´
5
J11´ JHH (para) 0.54 JAA´ 0.54 JBB´
N 8.85 8.85
L 6.17 6.17
K 8.94 8.94
M -6.86 6.86
K ≈ N > M > L
where set 1 again seems to be more likely than set 2. The corresponding spectrum was simulated
using the data given above:
712 708 704 700 696 692 688 684

(Hz)
1
Figure 356 : Simulated 100 MHz H NMR. 0.2 mol % in CS2. Ref. int. TMS. HWB = 0.35 Hz.
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8.15.7.3 Example 7c: [AB]2 and ABCD Overlay in Hexaphenylene – Atropisomer 2
The spectroscopic situation is more complicated for the second atropisomer 2 of ortho-
Hexaphenylene. For this isomer an overlay of [AB]2 and ABCD spectra in a ratio of 2:4 is expected.
NMR Parameters for [AB]2 Part from Rings A and D

ν1 723.77 νA 707.62 νB
ν2 707.62 νB 723.77 νA
3
4
3
J22´ JHH (ortho) 7.27 JBB´ 7.27 JAA´
5
J11´ JHH (para) 0.46 JAA´ 0.46 JBB´
N 9.31 9.31
L 6.35 6.35
K 7.73 7.73
M -6.73 6.73
N > K > M > L
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NMR Parameters for ABCD Part from Rings B, C, E and F
Parameter Type Set 1 Set 2

ν1 638.42 νD 648.53 νC
ν2 666.13 νB 674.63 νA
ν3 674.63 νA 666.13 νB
ν4 648.53 νC 638.42 νD
3
J12 JHH (ortho)´ 7.64 JBD 7.96
4
J13 JHH (meta) 1.52 JAD 130
5
J14 JHH (para) 0.45 JCD 0.45
3
J23 JHH (ortho) 7.34 JAB 7.34
4
J24 JHH (meta) 1.30 JBC 1.52
3
J34 JHH (ortho)´ 7.96 JAC 7.64
It is interesting to note that all protons from the ABCD part resonate to lower frequencies than
protons from the [AB]2 part. This is typical for “stacked” benzene rings. Many references are
available, e.g.: a) Janusenes: S. J. Cristol, D. C. Lewis; J. Amer. Chem. Soc. 89, 1476-1483 (1967);
b) [2.2]-para-Cyclophanes: M. Psiorz; Tetrahedron, 45, 1683-1689 (1989).
1
Figure 357 : Experimental 100 MHz H NMR. 1 mol % in CS2. [AB]2 part. Rings A and D. *)
Impurity: Sharp line from CHCl3.
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1
Figure 358 : Simulated 100 MHz H NMR as a “true” [AB]2 without long range couplings.
In practice this is not a true 4-spin system of type [AB]2. Line broadening and additional splittings in
5
the experimental spectrum indicate JHH long range couplings.
1
Figure 359 : Experimental 100 MHz H NMR. 1 mol % in CS2. ABCD part. Rings B, C, E, F.
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1
Figure 360 : Simulated 100 MHz H NMR. 1 mol % in CS2. ABCD part. Rings B, C, E, F.
Problems Involving Long Range Coupling 5JHH
5
Proton H1 from ring A (707.62 Hz) couples with proton H1 from ring B (648.53 Hz) with JHH= 0.28
Hz.
5
Proton H1´ from ring A (707.62 Hz) couples with proton H1 from ring F (648.53 Hz) with JHH= 0.28
Hz.
Analogous conclusions are valid for protons being symmetrically equivalent to the above mentioned
pair.
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Hence the full simulations should be performed by approximations:
a) [ABK]2 for the “[AB]2” part in rings A and D

b) ABCDKK´ for the ABCD part in rings B, C, E and F
Simulate those spectra with TopSpin / DAISY using the fragmentation technique.
The total spectrum – without the long range coupling – should look like
720 700 680 660 640

(Hz)
Figure 361 : Total spectrum without long range coupling
Try your hand with TopSpin / DAISY using the fragment tool for overlays of spectra.
8.15.8 [AX]2 – A Limiting Case of the [AB]2 System
Compare ortho-dibromobenzene o-C6H4Br2 (discussed above in class 1 compounds) and the

corresponding fluoro analogue ortho-dibromotetrafluorobenzene o-C6F4Br2:
H F
H Br F Br
H Br F Br
H F
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While ortho-dibromobenzene yields a neat [AB]2 system, ortho-dibromotetrafluorobenzene gives rise

19
to an [AX]2 spectrum (with very low [AB]2 character) at F NMR frequencies as low as 56.4 MHz.
The absolute values of coupling constants between fluorine spins are larger than those between
19
protons in adequate stereo-specific relations. But F spins are more sensitive to substituent effects
than protons, hence the difference in resonance frequencies ∆ν = νA-νB is large as well.
The 19F NMR Spectrum of 1,2-Dibromotetrafluorobenzene (10 % in CH3 CN)
Parameter Type Data [Hz]

νA νF 750.0
νB νF -750.0
3
JAB JFF(ortho) -21.0
4
JAB´ JAB(meta) 3.0
5
JAA´ JAA(para) 7.9
3
JBB´ JBB(ortho) -19.1
N -18.0
L -24.0
K -11.2
M 27.0
M > L > N > K
19
56.4 MHz F NMR Spectrum. Transition Frequencies and Intensities of the A Part
Parameters
in Sub-spectra
[AX]2 Analysis
1 781.657 0.242 L,M
2 768.894 0.563 L, K
3 759.057 1.976 N
4 759.054 1.976 N
5 757.696 1.408 L,K
6 754.660 1.736 L,M
7 745.532 1.758 L,M
8 742.412 1.437 L,K
9 741.095 2.024 N
10 741.054 2.024 N
11 731.214 0.592 L,K
12 718.535 0.264 L,M
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0.9
0.8
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0
790 785 780 775 770 765 760 755 750 745 740 735 730 725 720 715 710
[Hz]
19
Figure 362 : The A part of the 56.4 MHz F NMR spectrum of 1,2-dibromotetrafluorobenzene (10 % in
CH3CN).
19
For completeness sake the Dischler-Englert decomposition of this 56.4 MHz F NMR spectrum is
shown in the following graphics:
Dischler-Englert Assignment
b a
νC1 ≅ νA
Figure 363 : The N-lines a b (overlapping lines k and l resp.)
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D-F≅M G = L2 + M2
d e
c f
νC2
Figure 364 : Lines c d e f
E2-E3 K/2-E2-E3
i h
j g
νC3
Figure 365 : Lines g h i j
½K - E1 - E4 ≅ N
l k
Figure 366 : Lines k l (overlapping lines a and b resp.)
19
It is evident, that we do NOT need to perform the full Dischler-Englert analysis for F NMR spectra
measured at frequencies at (or higher than) 56.4 MHz from o-C6F4Br2. It suffices to follow the
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standard methods described for [AX]2 analysis, see table above. Iteration as [AB]2 does not
substantially improve resonance frequencies and coupling constants.
19
Steric strain and substituents affect the F NMR spectrum of o-C6F4R2.
Example: Tetrafluorophthalic Acid Anhydride.
F1 O
19 F2 C 19
84.66 MHz F NMR 470.3 MHz F NMR
an [AB]2 Spectrum O an [AX]2 Spectrum

F3 C
F4 O
Parameters Data
δ1 = δ4 δA = δA´ -131.8 [ppm]
δ2 = δ3 δB = δB´ -138.1 [ppm]
ν1 = ν 4 νA = νA´ -12399.3486 [Hz]
ν2 = ν 3 νB = νB´ -12992.0337 [Hz]

J12 = J34 JAB = JA´B´ -20.3 [Hz]
J13 = J24 JAB´ = JA´B 11.7 [Hz]
J14 JAA´ 17.3 [Hz]
J23 JBB´ -18.8 [Hz]
N N -8.6 [Hz]
L L -32.0 [Hz]
K K -1.5 [Hz]
M M 36.1 [Hz]
HWB HWB 0.3 [Hz]
M > L > N > K
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Corresponding simulations are shown below:
-12360 -12400 -12440

(Hz)
-12960 -13000 -13040

(Hz)
-12390 -12400
(Hz)
19
Figure 367 : Simulated 84.66 MHz F NMR spectrum. A part (upper). B part (middle). Expansion: 6 lines
in center of A part (lower).
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Transition frequencies and intensities of tetrafluorophthalic acid anhydride together with the
Dischler-Englert assignment are listed in the following table.:
Line DE Assign Frequency Intensity

[Hz] [rel.]
1 c -12356.7711 0.2189
2 g -12382.5648 0.9012
3 h -12384.0569 0.9949
4 d -12392.8184 1.7090
5 k -12394.6126 1.9670
6 a -12395.0174 1.9710
7 l -12403.2206 2.0249
8 b -12403.6174 2.0290
9 e -12405.0123 1.7811
10 i -12414.5780 1.1029
11 j -12416.0700 1.0091
12 f -12441.0596 0.2910
13 f´ -12950.3227 0.2910
14 j´ -12975.3123 1.0091
15 i´ -12976.8043 1.1029
16 e´ -12986.3700 1.7811
17 b´ -12987.7649 2.0290
18 l´ -12988.1617 2.0249
19 a´ -12996.3649 1.9710
20 k´ -12996.7697 1.9670
21 d´ -12998.5639 1.7090
22 h´ -13007.3254 0.9949
23 g´ -13008.8175 0.9012
24 c´ -13034.6112 0.2189
Comments: Solution in CDCl3. Concentration not specified in publication.

For details read:
I. P. Chuikov, D. S. Fadeev, V. I. Mamatyuk, T. A Vaganova, E. V. Malykhin; J. Fluorine. Chem. 132,
5121-515 (2011).
19
Exercise: Simulate the corresponding 470.3 MHz F NMR spectrum which appears as [AX]2 type.
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8.16 The [AB]2 System Part 2: p-Disubstituted Benzenes

Class 2: Asymmetrically 1,4-Disubstituted para-Benzene Derivatives
R1
H H
H H
R2
This class of [AB]2 spectra is characterized by N, L, K, and M parameters following:
[1] N ≈ L > K >> M
8.16.1 Example 1: 1H NMR Spectra of 1-Bromo-4-chlorobenzene
1
H NMR Spectra of 1-bromo-4-chlorobenzene at 500 MHz and 200 MHz exhibit a simple spectral
pattern.
60 40 20 0 -20 -40 -60

(Hz)
1
Figure 368 : Total 500 MHz H NMR spectrum of 1-bromo-4-chlorobenzene
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35 25 15 5 -5 -15 -25 -35

(Hz)
1
Figure 369 : Total 200 MHz H NMR spectrum of 1-bromo-4-chlorobenzene
55 50 45 25 20 15
(Hz) (Hz)
A part. 500 MHz. A part. 200 MHz.

Figure 370 : Expanded spectra, A parts. Left: 500 Hz. Right: 200 MHz
While the M,L-ab sub-spectrum (lines c d e f) is hidden below the N-lines, the K,L-ab sub-
spectrum (lines g h I j) is clearly visible. Hence parameters N, L and M are obtained with
agreeable accuracy. Lines k and l are almost degenerate with corresponding lines a and b resp.. K
will be accessible, but with reduced accuracy, by a line shape fitting program like TopSpin / DAISY.
Do not use a frequency fitting program of LAOCOON type. LAOCOON iteration for class 2 spectra
might go astray and fail convergence.
Read the critical comments from S. L. Mannat, “A caution regarding the use of LAOCOON III for
AA´BB´ spin systems”. Org. Magn. Res. 9, 224-228 (1977).
In practice starting parameters for the iteration of [AB]2 spectra from class 2 compounds are
obtained conveniently by [AX]2 approximation of spectra measured at high fields. In such situations
the full Dischler-Englert treatment is not required.
If we go back in time and down to low field spectrometers, we obtain more complicated spectral
structures and hence more interesting cases. This is true for the 60 MHz 1H NMR spectrum of
1-bromo-4-chlorobenzene (10% in CCl4) which will be studied in details below - for didactical
reasons. Follow the analysis and memorize the spectral patterns of para-disubstituted benzenes.
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1
60 MHz H NMR Parameters of 1-Bromo-4-chlorobenzene (10% in CCl4)
Br Br
H4 H1 HA´ HA
H3 H2 HB´ HB
Cl Cl
This [AB]2 Spectrum is Arbitrarily Centered Around νC = 0.

ν1 = ν 4 νA = νA´ + 6.0
ν2 = ν 3 νB = νB´ - 6.0
∆ν ∆ν 12.0
J12 JAB 8.7
J13 JAB´ 0.3
J14 JAA´ 2.3
J23 JBB´ 2.5
N 9.0
L 8.4
K 4.8
M -0.2
N > L > K >> M
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Transition Frequencies and Intensities - High Frequency Half Spectrum – A Part
Line DE Assign Frequency Intensity

[Hz] [rel.]
1 g 13.839 0.194
2 k 12.263 0.742
3 a 12.000 0.800
4 c 11.607 0.413
5 d 11.443 0.440
6 h 9.653 0.736
7 i 5.347 1.322
8 e 3.205 1.587
9 f 3.041 1.506
10 b 3.000 3.200
11 l 2.648 3.684
12 j 1.162 1.270
1
60 MHz H NMR Parameters of 1-Bromo-4-chlorobenzene (10% in CCl4)
15 12.5 10 7.5 5 2.5 0 -2.5 -5 -7.5 -10 -12.5 -15

[Hz]
Figure 371 : 60 MHz 1H NMR spectrum of 1-bromo-4-chlorobenzene (10% in CCl4)
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Decomposition of Transitions Following the Dischler-Englert Method
N C
b b´
a a´
15. 12. 9. 6. 3. 0. -3. -6. -9. -12. -15
[ Hz ]
Figure 372 : N-lines a and b
ef
cd
15. 12. 9. 6. 3. 0. -3. -6. -9. -12. -15
[ Hz ]
Figure 373 : (M,L)-lines c d e f . Separation D - F = c – d is not resolved.
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K/2-E2 - E3 E2 - E3
i j
15. 12. 9. 6. 3. 0. -3. -6. -9. -12. -15

νC3 [ Hz ]
K/2 - E1 - E4 E1 - E4 - C
l l´
k k´
15. 12. 9. 6. 3. 0. -3. -6. -9. -12. -15
[ Hz ]
Figure 375 : Lines k l
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8.16.2 Example 2: 1-Bromo-4-nitro-benzene
1
The H NMR spectrum of 1-bromo-4-nitro-benzene is a most suitable example for [AB]2 spectra of
class 2 with parameters following conditions: N ≈ L > K >> M
20.0 10.0 0.0 -10.0 -20.0
1
Figure 376 : H NMR spectrum of 1-bromo-4-nitro-benzene
NMR parameters of 1-bromo-4-nitro-benzene were found as listed below:
Parameter [Hz]
νA 11.724
νB -11.724
JAB = JA´B´ 8.822
JAB´ = JA´B 0.388
JAA´ 2.761
JBB´ 2.109
N 9.210
L 8.434
K 4.870
M 0.652
N > L > K >> M
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b,f,l
a,c,k
e
i
h
d j
2 0 .0 1 0 .0 0 .0 -1 0 .0 -2 0 .0
1
Figure 377 : Dischler-Englert assignment for H NMR spectrum of 1-bromo-4-nitro-benzene
Steps and Results in Dischler-Englert Analysis:
Groups Lines Results [Hz]

a, b a a 17.150
b b 7.940
∆1 23.338
νC1 12.545
N 9.210
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c, d, e, f c 17.030
d 16.350
e 8.520
f 7.940
∆2 23.448
νC2 12.460
M 0.651
G 8.460
L 8.435

g, h, i, j g 19.570
h 14.860
i 10.250
j 5.530
νC3 12.552

k, l k 17.150
l 7.780
T 0.160
K 4.870
Final Results
Parameter [Hz]
νA 11.724
νB -11.724
JAB = JA´B´ 8.822
JAB´ = JA´B 0.388
JAA´ 2.761
JBB´ 2.109
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8.16.3 Example 3: Some Halogenated 1,4-Disubstituted Benzene Derivatives
Results from NMR studies on some halogenated 1,4-disubstituted benzene derivatives are shown in
the following table.
R1
H H
H H
R4
All compounds shown below obey: N > L > K >> M
NMR Parameters for 1,4-Disubstituted Benzene Derivatives (δ[ppm], J[Hz])

1 4 1 4
Asymmetric p-C6H4R R Symmetric p-C6H4R R
R ≠R
1 4 1 4
R =R
1
R Cl Cl Br OMe Cl Br I
4
R Br I I Br Cl Br I
δB = δB´ δ2 = δ6 7.0705 6.9410 7.1478 6.5915 7.0702 7.2215 7.3058
δA = δA´ δ3 = δ5 7.2838 7.9785 7.4620 7.2070 7.0702 7.2215 7.3058

JAB = JA´B J23 = J56 8.54 8.41 8.39 8.74 8.55 8.41 8.26
JÁB´ = JA´B J25 = J36 0.33 0.33 0.30 0.27 0.39 0.46 0.33
JBB´ J26 2.49 2.54 2.40 3.09 2.58 2.38 2.21
JAA´ J35 2.47 2.22 2.36 2.55 2.58 2.38 2.21
N 8.87 8.74 8.69 9.01 8.94 8.87 8.53
L 8.21 8.08 8.09 8.47 8.16 7.95 7.93
K 4.96 4.76 4.76 5.64 5.16 5.74 4.42
M 0.02 0.32 0.04 0.54 0 0 0
For details read:

R. W. Crecely, J. M. Read, Jr., R. S. Butler, J. H. Goldstein; Spectrochim. Acta 24A, 685-694
(1968).
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8.16.4 Example 4: Para-substituted Benzoic Acids p-R-C6H4-COOH
COOH
H2 H6
H3 H5
R
1
Particular attention was drawn to para-substituted benzoic acids exhibiting [AB]2 spectra in H NMR
1 19
if R = Cl, Br, I. If R = F then [AB]2X is observed, which can be decoupled by H{ F} NMR to [AB]2.
The latter spectrum was approximated as [AX]2, see chapter 8.9.
Para-substituted Benzoic Acids
R Type F Cl Br I
δ2 = δ6 8.089 8.018 7.925 7.898 [ppm]
δ3 = δ5 7.304 7.543 7.707 7.765 [ppm]
∆δ 0.785 0.475 0.218 0.133 [ppm]

3
J23 = J56 JHH(ortho) 8.67 8.39 8.54 8.13 [Hz]
5
J25 = J36 JHH(para) 0.29 0.42 0.47 0.37 [Hz]
4
J26 JHH(meta) 2.77 2.22 2.21 1.94 [Hz]
4
J35 JHH(meta) 2.28 2.22 2.08 2.19 [Hz]
N 9.093 8.81 9.01 8.50 [Hz]
L 8.38 7.97 8.07 7.76 [Hz]
K 5.05 4.44 4.29 4.13 [Hz]
M 0.49 0 0.13 -0.25 [Hz]
All compounds listed above obey: N > L > K >> M
For details read:

1
R. H. Cox; Spectrochim. Acta 25A, 1189-1194 (1969). Results obtained from H NMR spectra of
para-hydroxy- and para-amino-benzoic acids were described by E. Evans, Jr., A. R. Tarpley and
J. H. Goldstein; J. Chem. Phys. 72, 2552-2556 (1968).
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Remarks
1) Chemical shifts are more sensitive towards substituent effects than coupling constants. Attempts
were made to correlate shifts with Hammet´s σ constants of substituents R.

3 4 5
2) The narrow expectation range for JHH(ortho) [8.1-8.7 Hz], JHH(meta) [1.9-3.1 Hz], and JHH(para)
[0.3-0.5 Hz] allows for an easy start of automated analysis with the line shape fitting program system
TopSpin / DAISY.
3
3) It might be useful to know: The ortho-coupling JHH from para-disubstituted halobenzenes C6H4XY
increases with the sum of electro negativities EX and EY of halogens X and Y:
3
JHH= 6.555 + 0.320 ⋅ (EX + EY )
Read:
A. R. Tarpley, H. B. Evans and J. H. Goldstein; Analytical Chemistry, 41, 402-406 (1969).
1 4
What do we expect from para-disubstituted tetrafluorobenzenes p-C6F4R R ?
R1
F F 4 1
F F 3 2
R4
Rudimentary 4-Spin Parameters for para-Disubstituted Tetrafluorobenzenes

1 4 1 4
Parameter R =H,R =H R =H,R =F Hypo*
δ1 = δ4
a b
-143 -138.89 ppm 0.1063*
δ2 = δ3
a b
-143 -162.06 ppm -0.1063*
J12 = J34 -20.736 -20.566 Hz -21*
J13 = J24 13.334 8.782 Hz 11*
J13 -0.224 -2.041 Hz -1.1*
J24 -0.224 -1.230 Hz -0.7*
N -7.042 -11.784 Hz -10*
L -34.070 -29.348 Hz -32*
K -0.448 -3.271 Hz -1.8*
M 0 -0.811 Hz -0.4*
Compounds shown above obey: L > N > K > M.
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References: Chemical Shifts
a) H. S. Gutowsky, D. W. McCall, B. R. McGarvey and L. H. Meyer; J. Amer. Chem. Soc. 74,

4809 (1952).
b) N. Boden, J. W. Emsley, J. Feeney and L. H. Sutcliffe; Mol. Phys. 8, 133 (1964). Coupling
constants:
c) V. Wray, L. Ernst and E. Lustig; J. Magn. Res. 27, 1-21 (1977).
Comments: Estimated parameters (*) for a hypothetical spectrum centered around νC = 0 Hz. ∆ν =
1 4 19
40 Hz. This case will be verified if R and R have similar substituent effects. The 188.154 MHz F
1 4
NMR spectrum of a hypothetical case p-C6F4R R is shown below.:
40 20 0 -20 -40
(Hz)
19 1 4
Figure 378 : 188.154 MHz F NMR spectrum of a hypothetical case p-C6F4R R .
8.17 The [AB]2 System Part 3: Ethane Fragments HFP

Part 3: 1,2-Disubstituted Ethanes and Related Structures

1 2 1 2 1 2
R -CH2-CH2-R , R -CF2-CF2-R , R -CP2-CP2-R
Class 3: K > N >> L > M [AB]2 spectra from rotating 1,2-disubstituted ethanes
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8.17.1 Example 1: 1-Bromo-2-chloroethane – Br-CH2 -CH2 -Cl
1 2
1-Bromo-2-chloroethane is a typical representative for compounds with R -CH2-CH2-R structures
which give rise to dynamic NMR spectra (at ambient temperatures) due to intra molecular rotation. A
simplified model for intramolecular rotation around the C-C axis uses canonical rotamers RI, RII and
RIII as shown below:
Cl Cl Cl
H4 Br H3 H4 Br H3
I II III
H1 H2 H1 H2 H1 H2
H3 Br H4
For di-halogenated ethanes trans-rotamer RII is more stable than the pair (of equivalent) gauche-
rotamers RI and RIII. This implies in terms of potential energy:
[1] E=I EIII > EII
[2] ∆E = EI − EII
From Boltzmann-distribution molar fractions xi for each rotamer are calculated:
∆E
−
RT
e
[3] x=I x=
III ∆E
−
1+ 2 e RT
1
[4] xII = ∆E
−
1+ 2 e RT
[5] xI + xII + xIII =

1
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The following table shows the distribution of rotamers as a function of ∆E at T = 293.15 °K.
Gauche Rotamer Trans Rotamer Gauche Rotamer

RI RII RIII
∆E(kcal/mol) xI xII xIII
0 0.3333 0.3333 0.3333
0.5 0.2294 0.5413 0.2294
1.0 0.1324 0.7358 0.1324
1.5 0.0660 0.8679 0.0660
2.0 0.0303 0.9394 0.0303
2.5 0.0133 0.9734 0.0133
3.0 0.0057 0.9886 0.0057
For Br-CH2-CH2-Cl in the gas phase ∆E was found to be ca. 1.5 kcal/mol. In solution ∆E will vary
with the type of solvent used for NMR samples. Each rotamer gives rise to individual NMR
parameters. This is illustrated for coupling constants in the following graphic:
Figure 379 : Rotamers I, II, and III and rotamer-specific coupling constants.
Rotamer specific parameters are listed below:
Rotamer Rotamer Specific Parameters
I Jg1 , Jg2 , Jg3 , Jt1

II Jg4 , Jt2
III Jg1 , Jg2 , Jg3 , Jt1
Hypothetically, 1-bromo-2-chloroethane under "frozen conditions" should exhibit 3 individual rotamer

specific spectra. Rotamers RI and RIII - the gauche forms – are responsible for ABCD type systems.
Since RI and RIII are mirror images to each other only one ABCD spectrum is expected (in the
isotropic phase). The trans rotamer RII gives rise to a symmetric [AB]2 system.
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For the equilibrium of rotational isomers we observe weighted averages of NMR parameters
following:
III
[6] < Pi > = ∑ x j p ij
j=I
where Pi stands for resonance frequencies νk and coupling constants Jkl (k = 1-4, l = 2-4, k < 1) as
shown in the subsequent table:
2
Resonance Frequencies and Geminal Coupling Constants JHH of Rotamers
2
Resonance Frequencies Coupling Constants JHH
RI RII RIII RI RII RIII
ν1 I ν1 II ν1 III J12 I J12 II J12 III
ν2 I ν2 II ν2 III
ν3 I ν3 II ν3 III J34 I J34 II J34 III
ν4 I ν4 II ν4 III
Taking into account symmetry:
[7] xI = xIII
[8] ν1I =ν 2 III
[9] ν 2 I =ν1 III
[9] ν3 I =ν 4 III
[10] ν 4 I =ν3 III
[11] J12 I = J12 III
[12] J34 I = J34 III
we can derive that the geminal pair of protons H1 and H2 in rotating Br-CH2-CH2-Cl are
isochronous.
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[13] < ν1 > = < ν 2 > = xI (ν1 I + ν1 III ) + xII ν1 II
[14] < ν 3 > = < ν 4 > = xI (ν 3 I + ν 3 III ) + xII ν 3 II
The averaged geminal coupling constants follow:
[15] < =
J12 > xI (J12 I + J12 III ) + xII J12 II
[16] < =
J34 > xI (J34 I + J34 III ) + xII J34 II
Following Figure 379 : four individual gauche coupling constants Jg(i) (i=1-4) and two individual
trans coupling constants Jt(i) (i=1,2), are defined in rotamers RI to RIII.
Taking into account symmetry leads to:
[17] < J13 > = < J24 > = xI (Jg2 + Jt1 ) + xII Jg4
[18] < J14 > = < J23 > = xI (Jg1 + Jg3 ) + xII Jt2
It is evident, that each pair of the geminal protons (H1, H2) and (H3, H4) is chemically equivalent
under conditions of free rotation. The correct description of this spin system is defined as [AB]2
(rot) :
H3 H1
Br C C Cl
H4 H2
[AB]2 (rot)
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Combining Rotational and Spectral Analysis
A very simplified model of intramolecular rotation assumes that all gauche coupling constants Jg
i
have identical values. And this assumption is made for trans coupling constants Jt as well:
i
[19] J=
g1 J=
g2 J=
g3 J=
g4 Jg
[20] J=
t1 J=
t2 Jt
which leads to some simplifications:
[21] < J13 > = < J24 > = xI (Jg + Jt ) + xII Jg
[22] < J14 > = < J23 > = 2 xI Jg + xII Jt
[23] < N > = < J13 > + < J14 > = xI (3 Jg + Jt ) + xII (Jg + Jt )
[24] < L > = < J13 > − < J14 > = (xII − xI ) ⋅ (Jg + Jt )
Combining the averaged values for N and L, obtained from direct analysis of the [AB]2 spectrum
leads to:
[25] 3 < N > + < L=

> 4 Jg + 2Jt
an expression which is independent from the actual distribution of rotamers. The averaged values
for weighted gauche and trans coupling constants result, numerically corresponding to a statistical
distribution of rotamers RI : RII : RIII = 1:1:1 (the high temperature limit). Check this by your own
calculations. This simplified model shows that <L> should approximate zero with increasing
temperature. The high temperature limit is defined by xI : xII : xIII = 1:1:1, where all three rotamers RI,
RII and RIII are equipopulated.
If
[26] < L > =0
then
2
[27] <=
N> (2 Jg + Jt )
3
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This simplified (and widely applied) model is useful for practical speculations concerning rotameric
equilibria. In an advanced status we will learn about more complicated descriptions of intra
molecular rotation.
Remember: NMR spectra of [AB]2 (rot) type are temperature dependent. Hence state clearly the
temperature of NMR samples in your lab notes and publications.
Example 1 for Class 3: K > N >> L > M
The 200 MHz 1H NMR Spectrum of 1-Bromo-2-chloroethane (5 % in C6H12)

Parameter Data [Hz]
νA 44.200
νB -44.200
JAB 5.600
JAB´ 10.650
JAA´ -9.856
JBB´ -10.792
N 16.250
L -5.050
K -20.648
M 0.936
K  > N  >> L > M 
1
Total 200 MHz H NMR Spectrum of 1-Bromo-2-chloroethane (5 % in C6H12).
70 60 50 40 30 20 10 0 -10 -20 -30 -40 -50 -60 -70

[Hz]
Figure 380 : 200 MHz 1H NMR spectrum of 1-bromo-2-chloroethane (5 % in C6H12).
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Four-Spin Systems
List of Transitions for the A Part.

Frequency Intensity
[Hz] [rel.]
65.874 0.009
53.066 1.638
52.330 1.676
47.307 0.763
46.373 1.125
45.384 1.899
44.498 1.943
42.171 1.237
41.237 0.875
36.816 2.362
36.238 2.412
24.007 0.051
200 MHz 1H NMR spectrum of 1-bromo-2-chloroethane (5 % in C6H12). A part.
The Dischler-Englert assignment is shown below:
bl
ih
ak
d e
c f
j g
70 65 60 55 50 45 40 35 30 25 20
[Hz]
Figure 381 : Dischler-Englert assignment for 200 MHz 1H NMR spectrum of 1-bromo-2-chloroethane (5
% in C6H12)
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Dischler-Englert Line Assignment

b
νC1
Figure 382 : Lines a b. The N-Lines.
e
d
f
c
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Four-Spin Systems
K/2-E2-E3 E2-E3
ih
g
j
Figure 385 : Lines k l
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Example 2 for Class 3: K > N >> L > M

1
For didactical reasons we will compare the above mentioned 200 MHz H NMR spectrum with the
corresponding 60 MHz 1H NMR spectrum of 1-bromo-2-chloroethane (5 % in C6H12) as shown
below.
60 MHz 1H NMR NMR Parameters for 1-Bromo-2-chloroethane (5 % in C6H12)
Parameter [Hz]
νA 6.630
νB -6.630
JAB 5.600
JAB´ 10.650
JAA´ -9.856
JBB´ -10.792
N 16.250
L -5.050
K -20.648
M 0.936
The four characteristic parameters obey:
K  > N  >> L > M 
A Part. High Frequency Half Spectrum

Frequency Intensity
22.269 0.027
18.612 0.450
14.468 0.459
14.148 0.796
10.745 0.011
10.102 0.499
9.227 0.796
6.506 1.625
4.966 1.501
4.091 1.204
2.362 3.550
1.296 5.078
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60 MHz 1H NMR Spectrum of 1-Bromo-2-chloroethane (5 % in C6H12)
25 20 15 10 5 0 -5 -10 -15 -20 -25

[Hz]
Figure 386 : 60 MHz 1H NMR of 1-bromo-2-chloroethane (5 % in C6H12)
N C
b b`
a a`
25 20 15 10 5 0 -5 -10 -15 -20 -25

[Hz]
Figure 387 : Lines a b b´ a´
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D-F G
ef
cd
25 20 15 10 5 0 -5 -10 -15 -20 -25

[Hz]
h i
g
j
25 20 15 10 5 0 -5 -10 -15 -20 -25

[Hz]
K/2 - E1 - E4 E1 - E4 - C
l l´
k k`
25 20 15 10 5 0 -5 -10 -15 -20 -25

[Hz]
Figure 390 : Lines k l l´ k´
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Solvent Effects and Spectral Appearance of [AB]2 (rot) Systems
In a preceding section we have derived the temperature dependence of NMR parameters for [AB]2
(rot) spectra. Solvent type and concentration influence the apparent NMR parameters as well.
Solvents of high dielectric constant favor the rotamer with the highest dipole moment.
This is shown with observations made for 60 MHz 1H NMR of 1-bromo-2-chloroethane comparing
solvents cyclohexane and dimethylformamide (DMF):
Parameter Type C6H12 DMF
δA 3.637 3.981 [ppm]
δB 3.416 3.793 [ppm]
∆δ 0.221 0.188 [ppm]

3
JAB JHH 5.600 6.195 [Hz]
3
JAB´ JHH 10.650 8.055 [Hz]
2
JAA´ JHH -9.865 -9.815 [Hz]
2
JBB´ JHH -10.792 -10.835 [Hz]
N 16.250 14.250 [Hz]
L 5.050 1.860 [Hz]
K 20.657 20.65 [Hz]
M 0.927 1.020 [Hz]
For solvents cyclohexane and dimethylformamide the four characteristic parameters obey:
K > N >> L > M and K > N >> L >≈ M
Basically the absolute values N and L decrease with increasing reaction field
parameter PRF which is a function of the dielectric constant εS of the actual solution:
εS − 1
[28] PRF =
εS + 2
εs depends on the dielectric constants (ε1, ε2) and volumes (V1, V2) of solvent (1) and solute (2):
εS − 1 ε1 − 1 V1 ε −1 V2
[29] = ⋅ + 2 ⋅
εS + 2 ε1 + 2 V1 + V2 ε2 + 2 V1 + V2
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For highly diluted solutions the parameter PRF approximates:
ε1 − 1
[30] PRF =
ε1 + 2
Hence state clearly solvent type and concentration (and temperature) of NMR samples in
your lab notes and publications.
Read more about reaction field theory, e. g. publications from the ABRAHAM group:
a) Chem. Comm. 1966, 588-589; b) Mol. Phys. 11, 471-494 (1966); c) J. Chem. Soc. (B) 1967, 202-
205; d) J. Chem. Soc. (B) 1969, 961-968; e) Org. Magn. Res. 6, 331-339 (1974); and papers quoted
herein.
Substituent Effects in Ethane like Structures R1-CH2-CH2-R2
1 2 1 2
Results from spectral and rotational analysis were described for R -CH2-CH2-R with R , R =
1
halogen (F, Cl, Br, I) and other substituents. Influences of electro negativities from substituent R
2 3
and R on vicinal coupling constants JHH are discussed.
For details read e.g.:

1) R. J. Abraham et al.:
a) J. Phys. Chem. 73, 1192 (1962);
b) J. Chem. Soc. (B) 1965, 435;
c) Z. phys. Chem. 58, 257 (1968);
d) J. Chem. Soc. (B) 1969, 961-968;
e) Mol. Phys. 11, 471 (1971).
2) W. C. Lin; J. Chem. Phys. 52, 2805-2814 (1970).
1
2,2-Dihalogeno-diethylethers (X-CH2-CH2)2O (X = Cl, Br, J) give rise to characteristic [AB]2 H NMR
spectra with K > N >> L ≈ M. Temperature- and solvent-effects were described by E.
Haloui, D. Canet and P. Granger; a) Org. Magn. Res. 3, 451-462 (1971), b) Org. Magn. Res. 4, 767-
778 (1972).
Bulky substituents favor the trans rotamers in a series tBu-CH2-CH2-X: xII(trans) and L increase with
X = F→Cl→Br→J, while ∆δ = δH(CH2-X) - δH(tBu-CH2) decreases in this order. Dominance of the
trans conformer is also found for tBu-CH2-CH2-Li.
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NMR Parameters for Some Selected Compounds tBu-CH2-CH2-X
Parameters Substituent X
F Cl Br I Li
∆δ 2.8667 1.735 1.445 1.2017 2.4267
JAB 6.5 11.3 12.1 13.0 15.5
JAB´ 6.5 3.4 5.1 4.8 3.5
JAA´ n.d. -13.6 -14.0 -13.6 -13.5
JBB´ n.d. -10.3 -9.9 -9.2 -12.1
N 13 14.7 17.2 17.8 19.0
L n.d. 7.9 7.0 8.2 12.0
K n.d. -23.9 -23.9 -22.9 -25.6
M n.d. -3.3 -4.1 -4.4 -1.4
Reference a a a a b
a) tBu-CH2-CH2-X, 20% in CCl4. 32°C. n.d. = not determined, deceptively simple triplets.
b) tBu-CH2-CH2-Li, in diethyl ether, -18°C. all examples: K > N >> L > M.
For details read:

a) G. M. Whitesides, J. P. Sevenair, R. W. Goetz; J. Amer. Chem. Soc. 88, 1135-114 (1967).
b) M. Witanowski, J. D. Roberts; J. Amer. Chem. Soc. 88, 737-740 (1966).
8.17.2 Fixing the -CH2-CH2- Skeleton in Rigid Ring Systems
1
The H NMR Spectrum of 2,2-Dibromocyclobutanone (10% in CCl4)
H A
O O
H Br B Br
H A´
H Br B´ Br
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Parameter Type Data

δA 3.40 [ppm]
δB 3.12 [ppm]
3
JAB JHH +11.16 [Hz]
3
JAB´ JHH +7.67 [Hz]
2
JAA´ JHH -15.31 [Hz]
2
JBB´ JHH -10.92 [Hz]
N 18.83 [Hz]
L 3.49 [Hz]
K -26.23 [Hz]
M -4.39 [Hz]
K > N >> L ≈ M
While the above mentioned sections dealt with vicinal couplings in dynamic systems here we find
data for JHH connected with a dihedral angle φ (H-C-C-H) of 0° and ca. 120° in rigid
3
conformation.
For details read: K. L. Servis, J. D. Roberts; J. Phys. Chem. 67, 2885-2886 (1963).
8.17.3 [AB]2 in the Fixed Conformation of a Meta-Cyclophane
H H4
H H3
H H2
H H1
The crystal structure and molecular geometry of meta-cyclophane was determined by X-ray
diffraction (C. J. Brown; J. Chem. Soc. 3278 (1953)). H. S. Gutowsky, X. Juan (Discuss. Faraday
Soc. 34, 52 (1962)) studied meta-cyclophane (10% solution in CCl4) at low fields using frequencies
as low as 60 MHz and 15 MHz. The 60 MHz spectrum showed an effective spectral half width of ca.
1 Hz. The difference of resonance frequencies for A- and B-nuclei and coupling constants
2 3 3
JHH(gem), JHH(trans), and JHH(gauche) were determined. Chemical shifts for A and B were not
2 3
stated. This early experiment deduced that the signs of geminal JHH and vicinal JHH coupling
1
constants are opposite. Here we will study a hypothetical 200 MHz H spectrum modifying data
given by Gutowsky and Juan.
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Four-Spin Systems

ν2 = ν 3 νA = νA´ +98.5
ν1 = ν 4 νB = νB´ -98.5
3
J12 = J34 JAB = JA´B´ JHH(gauche) 4.0
2
J13 = J34 JAB´ = JA´B JHH(gem) -12.0
3
J14 JBB´ JHH(trans) 12.3
3
J23 JAA´ JHH(gauche) 3.2
3 2
N JAB + JAB´ JHH(gauche) + JHH(gem) -8.0
3 2
L JAB - JAB´ JHH(gauche) - JHH(gem) 16.0
3 3
K JAA + JBB´ JHH(gauche) + JHH(trans) 15.5
3 3
M JAA - JBB´ JHH(gauche) - JHH(trans) -9.1
L ≈ K > M ≈ N
3 2
Since |N| < |L| sign of JHH(gauche) must be opposite to sign of JHH(gem) !
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1
Simulated 200 MHz H NMR Spectrum of meta-Cyclophane.
80 40 0 -40 -80
(Hz)
120 115 110 105 100 95 90 85 80

(Hz)
-80 -90 -100 -110 -120

(Hz)
Figure 391 : Simulated total spectrum of meta-cyclophane (global HWB = 0.3 Hz). Total spectrum (upper).
A part (middle). B part (lower).
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1
Simulated 200 MHz H NMR Spectrum of meta-Cyclophane
Lines Frequency Intensity Lines Frequency Intensity

1 117.4294 0.2543 13 -79.7330 0.3735
2 112.5635 0.4398 14 -85.0866 0.5812
3 103.4934 1.4188 15 -94.1567 1.5602
4 102.8060 1.9126 16 -94.5812 2.0812
5 102.5812 1.9188 17 -94.8476 2.0722
6 101.9710 1.6354 18 -95.1914 1.7519
7 95.1914 1.7519 19 -101.9710 1.6354
8 94.8476 2.0722 20 -102.5812 1.9188
9 94.5812 2.0812 21 -102.8060 1.9126
10 94.1567 1.5602 22 -103.4934 1.4188
11 85.0866 0.5812 23 -112.5635 0.4398
12 79.7330 0.3735 24 -117.4294 0.2543
1
Compare corresponding 60 MHz and 15 MHz H NMR spectra:
30 10 -10 -30 -50 35 25 15 5 -5 -15 -25 -35

(Hz) (Hz)
60 MHz 15 MHz
1
Figure 392 : 60 MHz (left) and 15 MHz (right) H NMR spectra. Global HWB = 1 Hz.
Remember: Basic ideas and results for NMR were shaped very early, despite less
advanced equipment. It is useful to read the early original NMR papers.
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8.17.4 Chirality and Spectral Pattern in the R1-CH2-CH2-R2 Skeleton
1 2
Chirality and spectral pattern in the R -CH2-CH2-R skeleton can be studied in the [AB]2 systems in
1 31
phosphorus decoupled H{ P} NMR spectra of meso and racem forms of (iPrO)(Ph)(O)P-CH2-CH2-
P(O)(Ph)(OiPr). Michaelis-Arbuzov reaction between BrCh2CH2Br and 2 PhP(OiC3H7)2 yielded two
stereo isomers which were characterized by X-ray diffraction studies.
Meso Racem
The P-C-C-P skeleton is in trans conformation for both stereo isomers giving rise to two different
1 31
[AB]2 systems when looking into the phosphorous decoupled proton H{ P} NMR spectra. The spin
assignments are shown in subsequent graphics:
B B´ B´ A´
O H H O O H H Ph
iPrO P C C P OiPr iPrO P C C P OiPr
Ph H H Ph Ph H H O
A A´ A B
Meso Racem
P* P*
B´ H H A´ A´ H H B´
A H H B A H H B
P* P*
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1 31
Corresponding 500 MHz H{ P} NMR spectra are shown below:
2.20 2.10 2.00 1.90

(ppm)
1 31
Figure 393 : 500 MHz H{ P} NMR spectrum of the meso isomer
2.20 2.10 2.00 1.90

(ppm)
1 31
Figure 394 : 500 MHz H{ P} NMR spectrum of the racem isomer
Parameters [Hz] Meso Racem

νA 1029.900 1071.870
νB 997.500 952.400
JAB = JA´B´ -15.151 -15.277
JAB´ = JA´B 3.852 13.469
JAA´ 13.690 4.132
JBB´ 13.690 3.456
∆ν 32.400 119.470
N -11.299 -1.808
L -19.003 -28.746
K 27.380 7.588
M 0.000 0.676
HWB 1.0 1.0
Meso K > L > N >> M - Racem L > K > N >≈ M
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NMR data found confirm the stereo chemical assignment of meso and racem forms. Try your hand
on a manual analysis of those [AB]2 NMR spectra using data given below:
1 31
Transition Frequencies and Intensities in 500 MHz H{ P} NMR
of Meso and Racem Forms
Meso Racem
Line Frequency Intensity Frequency Intensity Line
1090.2139 0.5623 1
1 1068.2947 0.0150 1088.2805 0.7445 2
2 1053.4943 0.0505 1087.6232 0.7877 3
3 1041.9808 0.9882 1082.8213 1.0495 4
4 1037.2555 1.2898 1074.4241 1.8922 5
5 1036.5077 1.3413 1072.8115 1.9359 6
6 1034.1402 1.3210 1072.7808 1.9697 7
7 1033.9804 0.5888 1070.9728 2.0303 8
8 1027.5741 1.9860 1060.9323 1.5152 9
9 1025.2067 2.6587 1059.5265 1.2555 10
10 1022.9798 3.0118 1058.8693 1.2123 11
11 1019.1800 2.7488 1053.5397 1.0448 12
12 1008.2200 2.7488 970.7303 1.0448 13

13 1004.4202 3.0118 965.4007 1.2123 14
14 1002.1933 2.6587 964.7435 1.2555 15
15 999.8259 1.9860 963.3377 1.5152 16
16 993.4196 0.5888 953.2972 2.0303 17
17 993.2598 1.3210 951.4892 1.9697 18
18 990.8923 1.3413 951.4585 1.9359 19
19 990.1445 1.2898 949.8459 1.8922 20
20 985.4192 0.9882 941.4487 1.0495 21
21 973.9057 0.0505 936.6468 0.7877 22
22 959.1053 0.0150 935.9895 0.7445 23
934.0561 0.5623 24
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8.17.5 R1-CF2-CF2-R2 - Fluorinated Analogues of R1-CH2-CH2-R2
Fluorinated ethanes have attracted considerable attention in stereo chemical and NMR
spectroscopic investigations. Interesting parameter combinations give rise to intricate spectral
patterns. Basic knowledge concerning intramolecular rotation was achieved using suitably
substituted perfluorinated compounds. A few examples are listed below.
For details read: L. Cavalli; J. Magn. Res. 6, 298-315 (1972).
F F
R1 C C R2
F F
1
R Br Br Br I I I I I I
2
R Cl Cl Cl Cl Cl Br Br Br Br
solvent a a c a d a b c c
T [°C] -40° 28° 80° -54° 28° 28° 28° 120° 134°
∆δ 1.8427 2.6249 3.7535 0.4761 4.1637 0.3029 0.3560 3.8508 4.0659
System* [AB]2 [AB]2 [AB]2 [AB]2 [AB]2 A2B2 [AB]2 A2X2 [AX]2
δA -68.04 -67.01 -67.01 -66.15 -62.88 -61.03 -60.95 -59.91 -57.25
δB -69.88 -69.63 -69.63 -66.94 -67.04 -61.33 -61.30 -63.73 -63.70

N -10.3 -10.55 -10.51 -14.2 -14.59 - -18.27 - -18.44
L -6.8 -4.97 -4.43 ca. -7 -2.35 - 0.93 - 1.62
K - - 347.4 - 384.0 - - - 373.8
M 8.9 6.95 3.43 42 - - 32.69 - -
Solvent: a) CH3COCH3. b) CH3COCH3/CH2ClCH2Cl, 10:1. c) C16H34.d) CH3COCH3/CCl4, 1:1.
35 37
Accidental symmetry of parameters: A2B2 : JAB = JAB´. A2X2 : JAX = JAX´. Cl / Cl isotope effects
were observed allowing for the unequivocal assignment of chemical shifts. *) For simplicity the
appendices (rot) for the rotating spin systems were omitted. Bear in mind: accidental higher
symmetry for A2B2 and A2X2. Some typical spectra of CF2I-CF2Br and CF2Br-CF2Cl are shown
below. For didactical reasons simulated spectra are centered around νC = 0. Examples obey
K >> M > N > L and K >> N > M > L.
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19
Simulated 94 MHz F NMR Spectrum of CF2J-CF2Br in Acetone at Room Temperature
20 10 0 -10 -20
(Hz)
19
Figure 395 : Simulated 94 MHz F NMR spectrum of CF2J-CF2Br in acetone at r. t.
19
NMR Data Used to Simulate the 94 MHz F NMR Spectrum of
CF2I-CF2Br in Acetone at r. t.:
Parameters Data [Hz] Temperature

ν1 = ν 4 14.2500 a
ν2 = ν 3 -14.2500 a
J12 = J34 -8.6700
J13 = J24 -9.6000
J14 203.2450
J23 170.5550
N -18.27 b
L 0.93 b
K 373.8 c
M 32.69 b
HWB 0.3
Temperature: a) 28°C (in acetone). b) 28°C (in solvent CH2COCH3 / CH2Cl-CH2Cl, 10:1).
c) auxiliary assumption, 134°C (in hexadecane).
K >> M > N >> L.
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Simulated Transition Frequencies and Intensities for CF2I-CF2Br in Acetone at r. t.:
Line Frequency [Hz] Intensity [rel.]

1 40.1162 0.0068
2 26.0616 0.9206
3 22.8824 1.1736
4 18.5788 1.2784
5 18.4976 0.0180
6 15.2745 1.7403
7 14.2469 1.9999
8 14.2056 1.9820
9 7.7916 3.0794
10 6.2629 3.8001
11 -6.2629 3.8001
12 -7.7916 3.0794
13 -14.2056 1.9820
14 -14.2469 1.9999
15 -15.2745 1.7403
16 -18.4976 0.0180
17 -18.5788 1.2784
18 -22.8824 1.1736
19 -26.0616 0.9206
20 -40.1162 0.0068
Effectively only 14 lines are observed. Try retro-analysis using the Dischler-Englert method.
Remarks: If you compare Cavalli´s experimental spectrum with your own simulation or with Figure
395 : (shown above), you will detect that the experimental N-Lines are sharper than the rest of the
transition lines in this [AB]2. The experimental peak heights of those N-lines are higher than the
calculated ones.
Note: N-lines have smaller values for spectral half widths than the other lines. This
phenomenon is also found for N-Lines in [AX]2 and [AXn]2 cases (to be discussed later). Lorentzian
generators with line specific spectral half widths are needed for good simulations. Hence write
your own simulator!
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19
Simulated 94 MHz F NMR Spectrum of CF2I-CF2Br in Hexadecane at 120°C
Approximating a Deceptively Simple Triplet
150 50 -50 -150

(Hz)
19
Figure 396 : Simulated 94 MHz F NMR spectrum of CF2I-CF2Br in hexadecane at 120°C.
19
CF2I-CF2Br in Hexadecane at 120°C

ν1 = ν 4 156.00 a
ν2 = ν 3 -156.00 a
J12 = J34 -8.41
J13 = J24 -10.03
J14 203.245
J23 170.555
N -18.44 b
L 1.62 b
K 373.8 b
M 32.69 c
HWB 1.0
Temperature: a) 120°C (in hexadecane). b) 134°C (in hexadecane). c) auxiliary assumption, 28°C
(in solvent CH2COCH3 / CH2Cl-CH2Cl, 10:1).
K >> M > N >> L.
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19
Simulated 94 MHz F NMR Spectrum of CF2I-CF2Br in Hexadecane at 120°C

1 188.7120 0.0010
2 165.4922 1.8820
3 165.2133 1.8869
4 156.2901 1.9944
5 156.2544 1.9951
6 156.0224 1.9985
7 155.9818 1.9990
8 147.0522 2.1180
9 146.7797 2.1234
10 123.2923 0.0015
11 -123.2923 0.0015
12 -146.7797 2.1234
13 -147.0522 2.1180
14 -155.9818 1.9990
15 -156.0224 1.9985
16 -156.2544 1.9951
17 -156.2901 1.9944
18 -165.2133 1.8869
19 -165.4922 1.8820
20 -188.7120 0.0010
Four weak lines are obscured, 16 lines should be observed but appear basically as a triplet for A
and B parts. Only νA, νB and approximately N may be extracted from this spectrum.
19
Remember: F chemical shifts are very sensitive to substituent-, temperature- and solvent-effects.
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19
Simulated 94 MHz F NMR Spectrum of CF2Br-CF2Cl in Acetone at Room Temperature
130 125 120 115

(Hz)
-115 -120 -125 -130

(Hz)
-115 -120 -125 -130

(Hz)
19
Figure 397 : 94 MHz F NMR spectrum of CF2Br-CF2Cl in acetone at room temperature.
35 37 35 37
A part (upper), hypothetical B part without Cl/ Cl isotope effect (middle), and B part with Cl/ Cl
isotope effect (lower).
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35 37
Note: The Cl/ Cl isotope effect in the CF2Cl resonances allows for a unique assignment of A- and
B-signals to CF2Br and CF2Cl groups.
Look into the simulated A part (CF2Br) shown above, which appears as a seven-line system. An
[AX]2 approximation leads to parameters νA, N, L and M. K is not accessible by direct analysis. The
very weak outer lines of the (K,L) sub-spectrum are not visible.
Iteration with a line-shape-fitting program (TopSpin / DAISY) will help – when supported by an
educated guess for starting values of K.
19
CF2Br-CF2Cl in Acetone at Room Temperature

ν1 = ν 4 123.5000 a
ν2 = ν 3 -123.5000 a
J12 = J34 -7.7600
J13 = J24 -2.7900
J14 177.1750
J23 170.2250
N -10.55 a
L -4.97 a
K 347.4 b
M 6.95 a
HWB 0.3
Temperature: a) 28°C (in acetone). b) auxiliary assumption; 80°C (in hexadecane).
K >> N > M > L.
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19
94 MHz F NMR Spectrum of CF2Br-CF2Cl in Acetone at r. t.
35 37
Simulated as A Part (upper) and Hypothetical B Part without Cl/ Cl Isotope Effect.
1 131.2714 0.1754
2 128.8876 1.9147
3 128.7834 1.9171
4 124.3228 1.8012
5 123.6352 1.9968
6 123.5900 1.9976
7 122.7272 1.8246
8 118.3376 2.0853
9 118.1716 2.0881
10 115.7786 0.1988
11 -115.7786 0.1988
12 -118.1716 2.0881
13 -118.3376 2.0853
14 -122.7272 1.8246
15 -123.5900 1.9976
16 -123.6352 1.9968
17 -124.3228 1.8012
18 -128.7834 1.9171
19 -128.8876 1.9147
20 -131.2714 0.1754
8.17.6 Rigid Skeleton -CF2-CF2- in Substituted Perfluoro Cylobutenes
F
R1
C C
F
F
C C
F R1
A wide series of compounds (e. g. with R , R = F, Cl, Br, I, H, CH3, P(O)(OCH3)2; R = R , R ≠ R )

1 2 1 2 1 2
and corresponding NMR data are known, but here it might be sufficient to discuss one typical case
1 2
where R = Br and R = Cl.
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NMR Parameters of 1-Bromo-2-chloro-3,3,4,4-tetrafluorocyclobutene C4F4BrCl
Parameter Parameter [Hz]

δ1 = δ2 δA 46.125
δ1 = δ2 δA 45.089
∆δ δA - δB 2.6249
ν1 = ν 2 νA 4339.3015
ν3 = ν 4 νB 4241.8377
2
J12 JFF (AA´) 190.7100
3
J13 = J24 JFF (AB) -13.2700
3
J14 = J23 JFF (AB´) 24.7900
2
J34 JFF (BB´) 190.1900
N 11.52
L -38.06
K 380.90
M 0.52
HWB HWB 0.3000
Note: For this example the chemical shifts δF of CF2 groups refer to δF(C6F6) = 0 ppm from internal
C6F6.
K >> L > N >> M.
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19
94.1 MHz F NMR Spectrum of C4F4BrCl.
46.4 46.0 45.6 45.2 44.8

(ppm)
4360 4350 4340 4330

(Hz)
4260 4250 4240 4230 4220

(Hz)
19
Figure 398 : 94.1 MHz F NMR spectrum of C4F4BrCl. Total spectrum (upper). A part (middle). B part
(lower).
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Four-Spin Systems
Remember the typical spectral pattern. Characteristic NMR parameters are given above and a table
holding transition frequencies and intensities is shown below.

1 4362.1594 0.6252
2 4361.6750 0.6473
3 4345.4007 1.7652
4 4343.6219 1.8242
5 4340.5565 1.9404
6 4338.7249 2.0129
7 4334.2437 2.2216
8 4333.8807 2.2348
9 4324.0959 1.3748
10 4323.6115 1.3527
11 4257.5277 1.3527
12 4257.0433 1.3748
13 4247.2585 2.2348
14 4246.8955 2.2216
15 4242.4143 2.0129
16 4240.5827 1.9404
17 4237.5173 1.8242
18 4235.7385 1.7652
19 4219.4642 0.6473
20 4218.9798 0.6252
Exercise: Analyze this spectrum. Only 10 lines for each half spectrum are detected. Again the weak
outer lines for the (K,L) sub-spectrum are not detected. Hence, direct analysis will lead to
parameters νA, νB, N, L and M only.
For details read: G. Bauer und G. Hägele; Z. f. Naturforsch. 34b, 1252 (1979)
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8.17.7 H-CP*2-CP*2-H - Phospha Analogues of R1-CH2-CH2-R2
1,1,2,2-Ethane-tetrakis-(P-phenyl-phosphinic acid)-tetraisopropylester CHP*2-CHP*2 (P* =

P(Ph)(O)OiPr) has 4 centers of chirality in P*. One of the stereo isomers gives rise to an [AB]2
31 1
system in proton decoupled P{ H} NMR.
Parameter Parameter Parameter [Hz]

ν1 = ν 4 νA νP 2951.615
ν2 = ν 3 νB νP 2551.346
∆ν νΑ - ν B 400.269
2
J12 = 34 JAB JPP(gem) 20.414
3
J13 = 23 JAB´ JPP(gauche) 1.208
3
J14 JAA´ JPP(trans) 31.260
3
J23 JBB´ JPP(gauche) 16.173
N 21.622
L 19.206
K 47.433
M 15.087
K > N > L > M
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31 1
81 MHz P{ H} NMR. 5 % in CD3OD.
37.5 36.0 34.5 33.0 31.5

(ppm)
3000 2980 2960 2940 2920 2900

(Hz)
2600 2580 2560 2540 2520 2500

(Hz)
31 1
Figure 399 : 81 MHz P{ H} NMR spectrum of H-CP*2-CP*2-H (5 % in CD3OD). Total spectrum (upper). A
part (middle). B part (lower).
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1 3001.1435 0.0577
2 2971.5892 0.3466
3 2962.7150 1.8921
4 2962.6826 1.8924
5 2956.5195 1.5778
6 2953.7622 1.9053
7 2950.0458 1.9408
8 2947.1660 1.6534
9 2941.0930 2.1079
10 2941.0089 2.1094
11 2932.0964 0.4222
12 2902.6645 0.0944
13 2600.2897 0.0944
14 2570.8578 0.4222
15 2561.9453 2.1094
16 2561.8612 2.1079
17 2555.7882 1.6534
18 2552.9084 1.9408
19 2549.1920 1.9053
20 2546.4347 1.5778
21 2540.2716 1.8924
22 2540.2392 1.8921
23 2531.3650 0.3466
24 2501.8107 0.0577
This [AB]2 spectrum can be analyzed as [AX]2 and should be iterated as [AB]2.
31
We have seen similar patterns before involving nuclei other than P. Obviously typical spectral
patterns depend on typical numerical relations for parameter combinations - independent of nuclear
types. Hence memorize characteristic spectral patterns.
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Consider the conformation of such an overcrowded molecule. A distorted all-gauche conformation is

found similar to:
P1
H
P3
H P2
P4
This conformation is typical for CHR2-CHR2 structures and found for a variety of bulky substituents
R attached to C-C, Si-Si, P-P and similar skeletons. Barriers to intramolecular rotation are relatively
high. Conformations may be frozen at room temperature, as shown for the above mentioned case.
This is true e.g. for CHR*2-CHR*2 with R* = P(O)(OAlkyl)2. The octaalkylester of the parent
31 1
1,1,2,2-ethane-tetraphosphonic acid gives rise to [AB]2 in P{ H} NMR at ambient temperature.
Warming up leads to an increase of intramolecular exchange, a singlet [[A]2]2 (rot) is observed
corresponding to the free rotating system.
8.18 The [AB]2 System Part 4: Dioxolanes – Spin System No. 37
Class 4: Dioxolanes and Related Cyclic Structures with -CH2-CH2- Fragments
8.18.1 Example 1: Dioxolanes Undergo Dynamic Ring Inversion
R1
H4 H4
H1 H1 C R2
C O C O
C O C O
H3 C R1 H3
H2 H2
R2
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1 2
Hence the parent compound (R = R = H) gives rise to an [[A]2]2 singlet for the -CH2-CH2- fragment
at δH = 4.57 ppm. (The O-CH2-O methylene group is responsible for an A2 singlet at δH = 3.57 ppm).
If R ≠ R then the four protons from -CH2-CH2- form an [AB]2 system with a characteristic spectral
1 2
pattern. In a didactically useful paper ABRAHAM (J. Chem. Soc. 1965, 256-262) described the
1 2 1
spectral analysis of 2-Methyl-1,3-dioxolane (R = CH3, R = H) quoting the following H NMR
parameters:
Parameter Data
∆δ 0.165 ppm
JAB -7.5 Hz
JAB´ 6.0 Hz
JAA´ 7.1 Hz
JBB´ 7.1 Hz
N -1.5 Hz
L 13.5 Hz
K 14.2 Hz
M 0 Hz
K >≈ L >> N >≈ M
1
Comments: Data from 60 MHz H NMR analysis for a solution of 2-Methyl-1,3-dioxolane in
benzene. Accuracy of coupling constants ±0.1 Hz. Exercise: Simulate a corresponding 60 MHz H
1
NMR spectrum and compare simulations for higher spectrometer frequencies..
1
The A part of a simulated 500 MHz H NMR spectrum of 2-Methyl-1,3-dioxolane should look similar
to the next Figure. Transitions are listed in a table below.:
60 55 50 45 40 35 30 25
(Hz)
1
Figure 400 : Simulated 500 MHz H NMR spectrum of 2-methyl-1,3-dioxolane in benzene. Spectrum
centered around νC = 0. A part. HWB = 0.3 Hz.
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Four-Spin Systems
Line Frequency [Hz] Intensity [rel]

1 57.9613 0.1922
2 48.5486 1.6770
3 43.9475 1.6142
4 42.4776 1.9322
5 42.0068 1.9636
6 41.1638 1.9845
7 40.5068 2.0364
8 38.5661 1.8392
9 35.0486 2.3230
10 24.5524 0.4376
Try your hand on Dischler-Englert analysis of this simulated 500 MHz [AB]2 spectrum.
8.18.2 Example 2: Ethylenesulphite
H4 H4
H1 H1 S O
C O C O
C O C O
H3 S H3
H2 H2
O
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1
Simulated H NMR spectra of ethylenesulphite are shown below for 500 MHz, 200 MHz and 100
MHz spectrometer frequencies.:
0.20 0.10 -0.00 -0.10 -0.20

(ppm)
60 40 20 0 -20 -40 -60

(Hz)
35 25 15 5 -5 -15 -25 -35

(Hz)
Figure 401 : 1H NMR spectra of ethylenesulphite (15% in CDCl3) at 500 MHz (upper), 200 MHz (middle)
and 100 MHz (lower).
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100 MHz Parameters for Ethylenesulphite (15 % in CDCl3 )
Parameter [Hz] Parameter [Hz]

νA 16.265
νB -16.265
JAB 6.600 N -1.76
JAB´ -8.360 L 14.96
JAA´ 6.900 K 13.63
JBB´ 6.730 M 0.170
L >≈ K >> N >≈ M
Transitions and Intensities for High Frequency Half Spectrum. A Part.
Line DE assign Frequency [Hz] Intensity [rel]

1 g 31.5694 0.1545
2 c 25.4603 0.5737
3 d 25.3058 0.5907
4 h 19.5278 1.3607
5 l 18.4274 1.7080
6 k 18.2558 1.5245
7 b 17.1688 1.8920
8 a 15.4088 2.1080
9 i 13.0498 2.0264
10 e 10.4993 1.4263
11 f 10.3449 1.4093
12 j 1.0082 1.2223
(1 additional weak line is calculated: 50.8334 Hz, 0.0030 rel. int.)
Exercise: Analyze the 100 MHz 1H NMR spectrum of ethylenesulphite listed above using the
Dischler-Englert assignments shown in the following figures:
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Four-Spin Systems
l
ef
a
i
b
cd
30 20 10 0 -10 -20 -30

[Hz]
Figure 402 : Total spectrum of ethylenesulphite 2
N C
a a’
b b’
νC1
Figure 403 : Lines a b
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Four-Spin Systems
ef
cd
νC1
Figure 404 : Lines c d e f . Splitting in pairs (c,d) and (e,f) not resolved.
½K-E2-E3 E2-E3
h
j
νC3
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Four-Spin Systems
lk l´ k´
Figure 406 : Lines k l l´ k´ . Splitting in pairs (k,l) and (l´,k´) not resolved.
8.18.3 Example 3: 2-Oxo-2-chloro-1,3-dioxa-2-phospholane
Cl
H4 H4
H1 H1 P O
C O C O
C O C O
H3 P Cl H3
H2 H2
O
Ring inversion involving two conformers characterized by axial and equatorial P=O groups gives rise
1 1 31
to a dynamic [AB]2X H NMR spectrum. By decoupling the phosphorus in H{ P} NMR the residual
[AB]2 spectrum is obtained, which can be analyzed by methods shown above.
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8.19 The [AB]2 System Part 5: Final Remarks

In preceding chapters we have dealt with [AB]2 type spectra subdivided into four classical cases:
Part Topic Part Topic

1 Ortho Benzenes 3 Ethane fragments
2 Para Benzenes 4 Dioxolanes
A few additional cases attract our attention and will be described in the following sections.
8.19.1 [AB]2 and A2B2 Systems in Isomeric Cyclobutanes
UV-induced cyclodimerisation of crystalline trans cynnamic acid leads to α-truxillic acid. This trans-
1,3-diphenyl-cyclobutane-trans-2,4-dicarboxylic acid and corresponding isomers (1 to 4) have
1 2
attracted attention in NMR spectroscopy. Those four [-CHR -CHR -]2 ring systems are characterized
by three different [AB]2 systems and one A2B2 system as shown below.
The Chemical Shifts δ [ppm] for [AB]2 and A2B2 Systems in 4 Isomeric Cyclobutanes
1 R1 R1 R1 H R1 H R1 R2
R = COOH
H H H R2 1 H R1 H H
2
R = C6H5 H H H R H R2 H H
R2 R2 R2 H R2 H R2 R1
Case 1 2 3 4
Symmetry Cs C2 C2v Ci
System [AB]2 [AB]2 A2B2 [AB]2
δA 4.5412 3.7339 4.4529 3.7288
δB 3.9888 3.1261 3.5671 3.2712
∆δ 0.5523 0.6078 0.8858 0.4576
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The Coupling Constants and Linearly Combined Parameters for [AB]2 and A2B2 Systems in 4
Isomeric Cyclobutanes
1 R1 R1 R1 H R1 H R1 R2
R = COOH
H H H R2 1 H R1 H H
2
R2 R2 R2 H R2 H R2 R1
Case 1 2 3 4
JAB 6.55 6.84 9.58 10.21
JAB´ 0.34 2.34 9.58 6.99
JAA´ 12.91 9.82 n.a. 0.04
JBB´ 0.10 8.90 n.a. 0.04
N 6.89 8.18 19.16 17.20
L 6.21 4.50 0 3.22
K 13.01 18.72 n.a. 0.08
M 12.81 0.92 n.a. 0.00
n.a. = not accessible in A2B2 system. Data given in Hz.
Cases 1, 2, and 4 obey the relations:
Case Relation
1 K >≈ M > N >≈ L
2 K >> N > L >> M
4 N >> L >> K ≈ M
Obviously the stereochemistry of those cyclobutane determines symmetry, origin and magnitude of
coupling constants and linearly combined parameters N, L, K, M and hence the total spectral
pattern.
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Stereochemical Coupling Constants and Linear Combinations
1
R1 R1 R1 H R1 H R1 R2
R = COOH
2
R = C6H5 H H H R2 1 H R1 H H
H H H R H R2 H H
R2 R2 R2 H R2 H R2 R1
Case 1 2 3 4
JAB 3 trans 3 trans 3 trans 3 cis

JHH JHH JHH JHH
JAB´ 4 trans 4 cis 3 trans 3 trans
JHH JHH JHH JHH
JAA´ 3 cis 3 trans 4 cis 4 trans
JHH JHH JHH JHH
JBB´ 3 cis 3 trans 4 cis 4 trans
JHH JHH JHH JHH
3 trans 4 trans 3 trans 3 cis 3 trans 3 trans 3 trans 3 cis

N JHH + JHH JHH + JHH JHH + JHH JHH + JHH
3 trans 4 trans 3 trans 4 cis 3 trans 3 trans 3 trans 3 cis
L JHH - JHH JHH - JHH JHH - JHH JHH - JHH
3 cis 3 trans 3 trans 3 trans 4 cis 4 cis 4 trans 4 trans
K JHH + JHH JHH + JHH JHH + JHH JHH + JHH
3 cis 3 trans 3 trans 3 trans 4 cis 4 cis 4 trans 4 trans
M JHH - JHH JHH - JHH JHH - JHH JHH - JHH
C2V symmetry in compound 3 gives rise to A2B2.
For details read:

a) G. Montaudo, S. Caccamese, V. Librando; Org. Magn. Res. 6, 534-536 (1974).
b) G. Montaudo, S. Caccamese; J. Org. Chem. 38, 710-716 (1973).
Exercise: Simulate those spectra using data given above and memorize patterns.
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1
In addition look into the (centered) H NMR spectra of corresponding bis-dimethyl-amides
1 2
(R = CON(CH3)2, R = C6H5):
1 R1 R1 R1 H R1 H R1 R2
R =
CON(CH3)2
H H H R2 1 H R1 H H
2
R2 R2 R2 H R2 H R2 R1
No. 5 6 7 8
∆δ 0.4715 0.0167 0.5660 0.8543
JAB 5.02 6.15 9.21 10.49
JAB´ 0.82 2.83 9.21 6.62
JAA´ 6.54 7.22 n.a. -1.06
JBB´ 2.90 7.22 n.a. -1.08
n.a. = not accessible in A2B2 system.
Parameters given by the above mentioned authors fit agreeably cyclobutanes 7 and 8 but not too
well compounds 5 und 6, as you will find out by simulation using DAISY or other suitable programs.
Originally data were obtained iterating on frequencies using a LAOCOON type program. A
reinvestigation with a line shape fitting program (TopSpin / DAISY) might be useful.
Conclusion: It is imperative to take explicit notes on sample preparation, acquisition,

processing and evaluation parameters of your spectra.
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1
8.19.2 H NMR Spectra of Dichloro-1,3-butadienes
1 3
Enumeration
C C 5
of stereo specific positions
2 C C
in butadiene derivatives
4 6
1
Four different stereo isomers of dichloro-1,3-butadienes were studied by H NMR, which gave rise
to three [AB]2 spectra and one ABCD spectrum.
Compounds are labeled according to stereo positions of chlorine atoms: 34, 16, 25, and 15
corresponding to the gem,gem-, trans,trans-, cis,cis-, and trans,cis-isomers:
H Cl Cl H H H Cl H
Iso C C H C C H C C Cl C C Cl
Pos. H C C H C C Cl C C H C C
Cl H H Cl H H H H
ClCl 34 16 25 15
HH,HH gem,gem trans,trans cis,cis trans,cis
System [AB]2 [AB]2 [AB]2 ABCD
For details read:
a) A. A. Bothner-By and R. K. Harris; J. Amer. Chem. Soc. 87, 3445-3450 (1965)

b) A. A. Bothner-By and R. K. Harris; J. Amer. Chem. Soc. 87, 3451-3453 (1965)
c) R. T. Hobgood and J. H. Goldstein; Mol. Spectr. 12, 76-86 (1964)
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1
NMR data from those references were used to simulate 200 MHz H NMR spectra as shown below:
1
H NMR Parameters of Dichloro-1,3-butadienes
Parameter Type 34 16 25 15
gem,gem trans,trans cis,cis trans,cis

[AB]2 [AB]2 [AB]2 ABCD
δ1 5.5916 - 6.144 -
δ2 5.9993 6.170 - 6.375
δ3 - 6.333 6.689 6.884
δ4 - 6.333 6.689 6.252
δ5 5,9973 6.170 - -
δ6 5.5873 - 6.144 6.032

2
J12 JHH (gem) -1.70 - - -
3
J13 JHH (cis) - - 7.28 -
4
J14 JHH (t) - - -1.17 -
5
J15 JHH (tc) 0.55 - - -
5
J16 JHH (tt) 1.90 - 1.74 -
3
J23 JHH (trans) - 13.12 - 13.34
4
J24 JHH (c) - -0.69 - -0.71
5
J25 JHH (cc) 0.59 0.83 - -
5
J26 JHH (tc) 0.55 - - 0.76
3
J34 JHH (s) - 11.24 10.36 10.82
4
J35 JHH (c) - -0.69 - -
4
J36 JHH (t) - - -1.17 -1.19
3
J45 JHH (trans) - 13.12 - -
3
J46 JHH (cis) - - 7.28 7.24
2
J56 JHH (gem) -1.70 - - -
1
Inspect the following simulated 200 MHz H NMR spectra of dichloro-1,3-butadienes:
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1
Simulated 200 MHz H NMR Spectra of Dichloro-1,3-butadienes
6.8 6.6 6.4 6.2 6.0 5.8 5.6

(ppm)
Figure 407 : Case 34: gem,gem 2, 3-dichloro-1,3-butadiene
6.8 6.6 6.4 6.2 6.0 5.8 5.6

(ppm)
Figure 408 : Case 16: trans,trans 1,4-dichloro-1,3-butadiene
6.8 6.6 6.4 6.2 6.0 5.8 5.6

(ppm)
Figure 409 : Case 25: cis,cis 1,4-dichloro-1,3-butadiene
6.8 6.6 6.4 6.2 6.0 5.8 5.6

(ppm)
Figure 410 : Case 15: trans,cis 1,4-dichloro-1,3-butadiene
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Four-Spin Systems
Similar results were obtained from early NMR studies on dimethylmuconates:
3 Stereo Isomers of Dimethylmuconate MeOOC-CH=CH-CH=CH-COOMe
Parameter Type 25 16 15
cis,cis trans,trans trans cis
[AB]2 [AB]2 ABCD
δ1 5.88
δ2 6.21 6.21
δ3 7.87 7.33 7.34
δ4 7.87 7.33 6.50
δ5 6.21
δ6 5.88 5.80
2
J12 JHH (gem) - - -
3
J13 JHH (cis) 11.8
4
J14 JHH (t) -1.3
5
J15 JHH (tc)
5
J16 JHH (tt) 1.3
3
J23 JHH (trans) 11.2 14.8
4
J24 JHH (c) -0.7 ???
5
J25 JHH (cc) 0.6
5
J26 JHH (tc) 0
3
J34 JHH (s) 11.3 16.5 10.7
4
J35 JHH (c) -0.7
4
J36 JHH (t) -1.3 0
3
J45 JHH (trans) 11.2
3
J46 JHH (cis) 11.8 10.7
2
J56 JHH (gem) - - -
Read: J. A. Elvidge, L. M. Jackman; Proc. Chem. Soc. 1959, 89-90.
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19
8.19.3 F NMR Spectra of Tetrafluoro-1,3-butadienes
1 3
Enumeration
C C 5
of stereospecific positions
2 C C
in butadiene derivatives
4 6
It is interesting to compare the spectral patterns of standard H-butadienes with those of fluorinated
analogues. Three different stereo isomers of dichloro-tetrafluoro-1,3-butadi-enes were studied. Two
[AB]2 and one ABCD were expected, but in practice one [AB]2, one deceptively simple [AX]2 and
one AMRX were found.
In addition the non-chlorinated 1,1,4,4-tetrafluorobutadiene was investigated yielding the spectral

19 1
pattern of an [ABX]2 system. After decoupling the protons by F{ H} NMR an [AB]2 system resulted.
Compounds are labeled according to stereo positions of chlorine atoms: 34, 16, 25, and 15
corresponding to the gem,gem-, trans,trans-, cis,cis-, and trans,cis-isomers:
Some Fluorobutadienes
Iso F H Cl F F F Cl F
C C F C C F C C Cl C C Cl
Pos.
F C C F C C Cl C C F C C
H F F Cl F F F F
HH,ClCl 34 16 25 15
FF,FF gem,gem trans,trans cis,cis trans,cis
Expect. [AB]2 [AB]2 [AB]2 ABCD
Found [AB]2 [AB]2 d. s. [AX]2 AMRX
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1
NMR Data of H NMR Spectra of Tetrafluoro-1,3-butadienes
Parameter Type 34 16 25 15
gem,gem trans,trans cis,cis trans,cis
[AB]2 [AB]2 d. s. [AX]2 AMRX
δ1 91.8
δ2 107.6 105.4
δ3 155.2 139.3 153.2
δ4 155.2 139.2 140.2
δ5 107.6
δ6 91.6 92.8
∆δ 1.461 47.6 47.5
2
J12 JFF (gem) 36.6
3
J13 JFF (cis) 7.9*
4
J14 JFF (t) 7.9*
5
J15 JFF (tc) 8.0
5
J16 JFF (tt) 4.8 n.a.
3
J23 JFF (trans) ±132.9 133.8
J24
4
JFF (c)  14.2 14.5
5
J25 JFF (cc) 35.7 22.7
5
J26 JFF (tc) 8.0 5.85
3
J34 JFF (s) 34.4 n.a. 34.1
J35
4
JFF (c)  14.2
4
J36 JFF (t) 7.9* 3.6
3
J45 JFF (trans) ±132.9
3
J46 JFF (cis) 7.9* 11.5
2
J56 JFF (gem) 36.6
n. a. = not accessible from deceptively simple [AX]2. 16) L > N > K > M
19
NMR data from those references may be used to simulate 188.3 MHz F NMR spectra.
Question: Are coupling constants reported for 2,5-dichloro-1,1,4,4-tetrafluoro-1,3-buta-diene
correct?
For details read:

a) K. L. Service; J. Amer. Chem. Soc. 87, 1339-1344 (1965)
b) R. A. Baudet; J. Amer. Chem. Soc. 87, 1390 (1965)
c) P. Bladon, D. W. Sharp, J. M. Winfield; Spectrochim. Acta. 22, 343-344 (1966)
d) S. L. Manatt, M. T. Powers; J. Amer. Chem. Soc. 91, 4381-4394 (1969)
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Heterocyclic Compounds
A multitude of heterocyclic compounds holds structural elements correlated with [AB]2 systems.
Here it will be sufficient to look at the classical examples of thiophene and two pyridine derivatives.
8.19.4 The 1H NMR [AB]2 Spectrum of Thiophene (Solution in CCl4)
Parameter Type Data

δA = δA´ δH 6.7884 ppm
δB = δB´ δH 6.5449 ppm

3
JAB = JA´B´ JHH 1.025 Hz
4
JAB´ = JA´B JHH 5.125 Hz
4
JAA´ JHH 2.75 Hz
3
JBB´ JHH 3.45 Hz
3 4
N = JAB + JAB´ JHH + JHH 6.15 Hz
3 4
L = JAB - JAB´ JHH - JHH 4.10 Hz
4 3
K = JAA´ + JBB´ JHH + JHH 6.20 Hz
4 3
M = JAA´ - JBB´ JHH - JHH 0.70 Hz
K ≈ N > L > M
1365 1360 1355 1350 1315 1310 1305 1300

(Hz) (Hz)
1
Figure 411 : 500 MHz H NMR spectrum of thiophene in CCl4. A part (left). B part (right).
Analyze the 500 MHz spectrum as [AX] 2 system and iterate with TopSpin / DAISY as [AB]2 case.
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For didactical purposes look at the “historic” spectrum of thiophene taken at 60 MHz.:
410 400 390

(Hz)
1
Figure 412 : 60 MHz H NMR spectrum of thiophene.
For details read: E. W. Garbisch Jr.; J. Chem. Ed. 45, 480-493 (1968)
1
Compare the H NMR spectrum of furane - deceptively simple triplets in [AB]2 and [AX]2
systems
If
L2
< HWB
M
then the A- and B- or X-half-spectra appear as deceptively simple triplets. This situation is given for
furane:
H3 H2
H4 H1
O
1
Furane gives rise to a deceptively simple [AX]2 H NMR spectrum. Two 1:2:1 triplets are observed
situated at δH = 7.28 ppm (α-protons) and δH = 6.23 ppm (β-protons).
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The triplet splitting corresponds to N/2. A deeper investigation by ABRAHAM and BERNSTEIN
yielded coupling parameters:
Parameters Date [Hz]

JAB 1.80
JAB´ 0.80
JAA´ 1.55
JBB´ 3.53
N 2.60
L 1.00
K 5.03
M -1.98
K > N > M > L
1
For the analysis of deceptively simple spectra and the H NMR spectrum of furane see:
a) R. J. Abraham and H. J. Bernstein; Can. J. Chem. 39, 216-230 (1961);
b) B. Dischler and G. Englert; Z. Naturforschg. 16a, 1180-1190 (1961);
c) D. M. Grant, R. C. Hirst and H. S. Gutowsky; J. Chem. Phys. 38, 470-487 (1963).
Remember: The appearance of triplets does not imply magnetical equivalence of two neighboring
protons!
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1
8.19.5 H NMR [AB]2 Spectra of 4-Methoxypyridine and N-methyl-4-pyridone
OCH3 O
H H H H
H N H H N H
CH3
1 2
Parameter Parameter 1 2
δA 8.3910 7.6225 [ppm]
δB 6.9340 6.0990 [ppm]

3
JAB JHH 5.75 7.55 [Hz]
5
JAB´ JHH 0.60 0.15 [Hz]
4
JAA´ JHH -0.20 2.50 [Hz]
4
JBB´ JHH 2.60 2.85 [Hz]
N 6.35 7.70 [Hz]
L 5.15 7.40 [Hz]
K 2.40 5.35 [Hz]
M -2.80 -0.35 [Hz]
δCH3 3.8230 3.6200 [ppm]
1) N > L > M >≈ K 2) N >≈ L > K > M
1
Simulate 200 MHz H NMR spectra using the fragmentation technique in TopSpin / DAISY.
Fragment 1: four protons from [AB]2. Fragment 2: three protons from A3. No couplings between
[AB]2 protons and methyl group.
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1
200 MHz H NMR Spectra of 4-Methoxypyridine 1 and N-methyl-4-pyridone 2
8.0 7.0 6.0 5.0 4.0

(ppm)
8.0 7.0 6.0 5.0 4.0

(ppm)
1 1
Figure 413 : 200 MHz H NMR total spectrum of 4-methoxypyridine 1 (upper) and 200 MHz H NMR total
spectrum of N-methyl-4-pyridone 2 (lower).
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Expanded spectra of 4-methoxypyridine 1 and N-methyl-4-pyridone 2 are shown below.:
Expanded Spectra
1684 1680 1676 1672

(Hz)
1396 1392 1388 1384 1380

(Hz)
Figure 414 : 200 MHz of 4-methoxypyridine 1. A part (upper). B part (lower).
1532 1528 1524 1520 1516

(Hz)
1228 1224 1220 1216 1212

(Hz)
Figure 415 : 200 MHz of N-methyl-4-pyridone 2. A part (upper). B part (lower).
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Some Final Remarks Concerning [AB]2
The total material on the [AB]2 system presented here is rather long and laborious.
Do we really need to perform the Dischler-Englert procedure for ALL of our practical
spectra?
Clearly the answer is NO, and that for several reasons.
After having acquired a reasonable knowledge of spectral patterns of [AB]2 systems it will be easier
to recognize specific spectral cases and make an educated guess for starting parameters in
TopSpin / DAISY calculations.
In addition Sequential Simulations with TopSpin / DAISY will help to find a narrow range of
expectation values. This useful tool allows to simulate automatically a series of spectra generated
from NMR parameters (ν, J) varying between lower and upper values in defined steps.
Convergence of difficult experimental and calculated spectra will be made visible. Try your hand
with Sequential Simulations.
Iterative calculations based on line shape will approximate the final values rapidly.
Hence in many practical situations it will be possible to skip the Dischler-Englert procedure, adopt
parameters from known structures, and start directly with TopSpin / DAISY iterations.
TopSpin / DAISY takes into account symmetry of spin systems in order to speed up calculations.
Those facilities are most valuable for iterative calculations of larger spin systems bearing:
a) Chemical equivalence
b) Magnetical equivalence
c) Both types of equivalence simultaneously
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Some examples are shown below:
Case Systems
a [AB]2, [AX]2, [AB]2C, [AB]2X, [AX]2B, [ABC]2, [ABX]2, [AMX]2, [AX]n, [AB]n, etc.
b ABn, AnBm, ABnX, AnBmX, etc.
c [ABn]2, [ABn]3, [AXn]2, [AXn]3 etc.
Practically relevant examples and the handling of such cases with TopSpin / DAISY will be
discussed in book 2 of this manuscript.
Modern PCs are fast, and hence TopSpin / DAISY will tackle neatly many of the more complicated
cases. The symmetry tool will be useful for larger spin systems, but in practice does not save much
time for simulation when dealing with smaller systems. Use symmetry in TopSpin / DAISY for
iterations involving magnetical equivalence in composite particle and chemical equivalence
for ≥ 4-spin cases and particularly for all calculations concerning higher spin systems if applicable.
8.20 The A2B2 System – Spin System No. 40
Chocolate flavor is a complex mixture containing amongst other compounds isomeric cyclo-dimers
of cynnamic acid. One of those isomers is ε-truxyllic acid (Example 1 below). Tetrakis-cyclo-hexyl-
cyclopentaphosphine forms several types of complexes with chromiumpentacarbonyl units. One of
those complexes is shown as Example 2 below.
Both examples give rise to homonuclear A2B2 which will be discussed within this chapter:
Example 1 Example 2
1 31 1
H NMR Spectrum P{ H} NMR Spectrum
R H R
C C P P
H R R
H R´ R Cr(CO)5
C C P P
R´ H Cr(CO)5 R
R = C6H5. R´= COOH R = c-C6H11
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19
In addition A2B2 systems may occur by accidental symmetry. For example F NMR spectra of 1-
bromo-2-iodo-tetrafluorethane Br-CF2-CF2-I were analyzed successfully as A2B2 systems and not as
[AB]2 which initially was expected by molecular symmetry.
Accidentally the spin symmetry of this compound is higher than the molecular symmetry leading to
JAB = JAB´. Compare details in chapter 8.15 where further examples of X-CF2-CF2-Y molecules are
discussed.
The Analysis of A2B2 Spectra
H A 1 A
H H B B 3 4 B B
H A 2 A
If the following symmetry criteria within a four spin system hold,
[1] ν1 =ν 2 =ν A
[2] ν3 =ν 4 =νB
[3] J=
13 J=
14 J=
23 J=
24 JAB
then the pair of A nuclei is magnetically equivalent and forms an A2 composite particle. In analogy
hereto the B2 composite particle is established. Coupling constants inside composite particles do not
influence the spectral pattern of the A2B2 systems. Hence direct analysis of A2B2 spectra does not
yield information on JAA´ (J12) and JBB´ (J34).
For didactical purposes we will study the following hypothetical A2B2 system with
NMR Parameters
νA νB JAB HWB νC ∆ν
440 360 20 0.3 400 80 [Hz]
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Transitions Frequencies and Intensities
Line Line Frequency Intensity

[Hz] [rel.]
1 1 464.7214 1.1056
2 2 459.2195 1.2977
3 3 447.0444 1.5361
4 4 442.3983 1.8050
5 5 440.0000 4.0000
6 6 424.7214 2.8944
7 7 421.5425 3.3579
8 7´ 378.4575 3.3579
9 6´ 375.2786 2.8944
10 5´ 360.0000 4.0000
11 4´ 357.6017 1.8050
12 3´ 352.9556 1.5361
13 2´ 340.7805 1.2977
14 1´ 335.2786 1.1056
yielding
The Hypothetical A2B2 Spectrum
Figure 416 : Hypothetical A2B2 spectrum - line numbers used analytically are indicated.
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The typical A2B2 spectrum may exhibit up to 18 transitions, which are arranged in pairs
symmetrically around the central frequency νC
ν + νB
[4] ν C = A
2
In practice four lines correspond to very weak transitions (combination lines). Therefore, the
characteristic A2B2 spectrum in most situations will appear as a 14 line pattern.
The total A2B2 spectrum can be divided into two half-spectra symmetrically arranged around the
center frequency νc.
It is useful to enumerate transitions of the left half spectrum (high-frequency, low field) from left to
right with νi (i = 1 - 7), while the corresponding transitions of the right half spectrum (low frequency,
high field) will be enumerated from right to left by νi´ (i´ = 1´ - 7´).
The first relevant findings are:
Lines ν5 and ν5´ resp. correspond directly to resonance frequencies νA and νB resp..
Lines ν1, ν6, ν6´ and ν1´ form a sub-spectrum of the general AB type with an apparent coupling J =
2 JAB.
Using expressions (known from AB analysis):
[5] So = ν1 − ν1´
[6] Si = ν 6 − ν 6´
[7] ∆ ν = ν A − νB
the following results are obtained:
ν +ν +ν +ν
[8] ν C = 1 6 6´ 1´
4
[9] ∆=
ν so ⋅ si
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S o − Si
[10] J =
2
∆ν
[11] ν A =ν C +
2
∆ν
[12] νB =ν C −
2
For completeness we may derive the four missing (non-detected) weak combination lines given by:
[13] νm1 =ν 2 + C
[14] νm2 =ν7 + C
[15] νm2´ =ν7´ − C
[16] νm1´ =ν 2´ − C
Hence calculate those four lines and look into the experimental spectrum with increased intensity
amplification. In suitable cases you may find some or all of those missing lines.
Some Practical Simplifications in A2B2 Spectral Analysis
Shift the experimental A2B2 spectrum to center it around zero and indicate the resulting, shifted
transition frequencies by asterisks *. Than
[17] ν∗C =0
[18] ν∗i = − ν∗i´ for all i from 1 to 7

7 7
[19]
=i 1=
∑ ν∗i + ∑ ν∗i´ =0
i´ 1
Under those conditions one half spectrum only is needed to calculate coupling constants. The
corresponding shifted resonance frequency follows:
[20] ν∗A = − νB∗ = ν∗5
ν1∗ − ν∗6
[21] JAB =
2
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Looking closer into details of the A2B2 spectrum two repeated spacings corresponding to 2 JAB are
found:
[22] ν1∗ − ν∗6 = ν∗6´ − ν1´∗ = 2JAB
In addition four repeated spacings are detected
[23] ν1∗ − ν∗6´ = ν∗3 − ν∗4´ = ν∗4 − ν∗3´ = ν∗6 − ν1´∗ = C

each corresponding to
[24] C = ∆ 2ν + 4 J2AB
For didactical purposes we will study an A2B2 system centered around νC = 0 Hz with
NMR Parameters
νA νB JAB HWB νC ∆ν
40 -40 20 0.3 0 80 [Hz]
giving rise to

[Hz] [rel.]
1 64.7214 1.1056
2 59.2195 1.2977
3 47.0444 1.5361
4 42.3983 1.8050
5 40.0000 4.0000
6 24.7214 2.8944
7 21.5425 3.3579
7´ -21.5425 3.3579
6´ -24.7214 2.8944
5´ -40.0000 4.0000
4´ -42.3983 1.8050
3´ -47.0444 1.5361
2´ -59.2195 1.2977
1´ -64.7214 1.1056
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as shown in the following plot:

The Centered A2B2 Spectrum
Intensity A2B2-System
ν*A ν*B
1 ∆ν
0.8 Si
0.6
2JAB C
0.4
S0
0.2
νC
0
80 70 60 50 40 30 20 10 0 -10 -20 -30 -40 -50 -60 -70 -80
[Hz]
1 3 4 6 6’ 4’ 3’ 1’
2 5 7 7 5 2
Figure 417 : The centered A2B2 spectrum.
Within the A part lines ν1∗ and ν∗6 and in addition lines ν∗3 and ν∗4 are centered in pairs around
ν C1 :
ν∗ + ν∗ ν∗ + ν∗ C
[25] νC1 = 1 6 = 3 4 =ν∗C +
2 2 2
In analogy for the B part is valid:
ν∗ + ν∗ ν∗ + ν∗ C
[26] ν C2 = 1´ 6´ = 3´ 4´ =ν∗C −
2 2 2
hence
[27] C = νC1 − νC2
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Limiting Cases of the A2B2 Problem
The spectral appearance of the A2B2 system is governed by the relation r
ν A − νB
[28] r =
JAB
If r is equal to or very close to zero, an A4 system is observed, a singlet.

With increasing size of ΙrΙ the A2B2 system will approximate the spectral habitus of an A2X2 case:
IrI <<1 IrI >>1

A 4 ← A 2B2 → A 2 X2
Some Remarks to Relations between A2B2, AB, and 1A1B Spectra
An A2B2 spectrum may be broken down into three separate sub-spectra:

a) the A2 singlet,
b) the B2 singlet,
1 1
c) an A B multiplet.
The latter case corresponds to a sub-system holding two spins with I = 1. (e. g.: two deuterons in
asymmetric fragments like D-C-D or D-C-C-D.
Visualization of the Decomposition of the A2B2 Spectrum
70 50 30 10 -10 -30 -50 -70

(Hz)
Figure 418 : The total A2B2 spectrum with J = JAB
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Figure 419 : The singlet lines at νA and νB
1 1
Figure 420 : The A B sub-spectrum with J = JAB
Figure 421 : The AB sub-sub-spectrum with J = 2 JAB
Two very weak combination lines were calculated:
Frequency Intensity
[Hz] [rel.]
110.985 0.003
-110.985 0.003
which might be overlooked in an experimental spectrum.
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8.21 The AB3 Spectrum and the Related A3B Case

AB3 and A3B type spectra were observed very early in NMR history. While methylmercaptane
CH3SH exhibits A3B, methanol CH3OH gives rise to AB3, as shown below. Methylacetylene
CH3CΞCH has a very small difference in chemical shifts of CH3 and CH groups and a small coupling
4
constant JHH. At low frequencies (in the early days of NMR) it was difficult to separate the individual
transition frequencies, thus CH3CΞCH effectively appeared as an A3A´ case. But later on
measurements with high resolution and at high frequencies revealed the A3B character.
1
5 mol% CH3OH together with 5 mol% H2O were dissolved in dimethylsulfoxide. The 60 MHz H
NMR spectrum of this solution is characteristic for an AB3 spin system: a quartet at δH(OH) = 4.08
ppm, and a doublet at δH(CH3) = 3.17 ppm. Observe the second order character of AB3 in CH3OH.
In addition a singlet for H2O is detected.:
1
Figure 422 : 60 MHz H NMR spectrum of a solution in dimethylsulfoxide holding 5 mol% CH3OH and 5
mol% H2O. (Simulated in analogy to data and graphic given by O. L. Chapman and R. W. King; J.
Amer. Chem. Soc. 86, 1256 (1964)).
While the proton transfer in water is fast, methanol undergoes a slow proton exchange:
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3
Hence the splitting by JHCOH in CH3OH is visible, giving rise to the AB3 case. Dissolving methanol in
H2O and adding a trace of HCl leads to rapid proton exchange with loss of coupling. Than a singlet
is seen for the methyl group.
Pure methanol at -65°C gives rise to an AB3 spectrum (AX3 at higher fields). Warming up to +37°C
induces a total collapse of the multiplet structures. Two singlets result for the OH and CH3 groups.
Read:
a) H. Günther, “NMR-Spektroskopie”, p. 224, Georg Thieme Verlag Stuttgart, New York, 1983.
b) H. Günther, “NMR-Spektroscopy”, p. 237, John Wiley Sons, Chichester, New York, Brisbane,
Toronto, 1980.
1 2 1 2 3
Further AB3 systems occur in CH3-CHR R and CH3-CH=CR R structures involving JHH couplings.
At higher fields AX3 cases are monitored. E. g.: CH3CHCl2. δH(CH3) = 2.1 ppm. δH(CH) = 5.9 ppm.
3
JHH = 6.1 Hz.
8.21.1 Practical Examples
Organo fluorine chemistry provides a palette of suitable model systems for NMR studies. An
interesting case of AB3 and A3B spin systems is observed for the pair of cis- and trans-isomers of
CFCl=CCl-CF3.
Cis- and Trans 1,2-Dichloro-1,3,3,3-tetrafluoro-prop-(1)-ene
Cl Cl F Cl
C C C C
F CF3 Cl CF3
AB3 A3B
19
F NMR Data of CF3-CCl=CClF
Parameter Type Data Type Data

δ1 δF (CF) A -18.4 δF (CF) B -25.0 ppm
δ2 δF (CF3) B3 -23.5 δF (CF3) A3 -23.7 ppm

4 4
J12 JFF (cis) 24.4 JFF (trans) 10.4 Hz
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19
Simulated 188 MHz F NMR Spectra
-19.5 -21.0 -22.5 -24.0

(ppm)
Figure 423 : AB3 spectrum of cis-CF3-CCl=CClF.
-18 -19 -20 -21 -22 -23 -24 -25

(ppm)
Figure 424 : A3B spectrum of trans-CF3-CCl=CClF
Expansions are shown below. Memorize the lines indicated by red arrows for spectral analysis.
Figure 425 : AB3 spectrum of cis-CF3-CCl=CClF. A part.
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Figure 426 : AB3 spectrum of cis-CF3-CCl=CClF. B3 part.
Figure 427 : AB3 spectrum of cis-CF3-CCl=CClF. B3 part. Expanded. See triplets.
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Figure 428 : A3B spectrum of trans-CF3-CCl=CClF. A3 part.
Figure 429 : A3B spectrum of trans-CF3-CCl=CClF. A3 part. Expanded. See triplets.
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Figure 430 : A3B spectrum of trans-CF3-CCl=CClF. B part.
8.21.2 Analyzing AB3 Type Spectra
While A is a single spin with I = ½ (DA), B3 represents a composite particle with a total spin
Fmax = 3/2. The composite particle B3 can be decomposed into two particles with F = ½ (DB) and
F = 3/2 (QB) affiliated with statistical weights g(F = 1/2) = 3 and g(F = 3/2) = 1.
Hence two separate sub-spectra are expected from DADB and DAQB. To solve the AB3 problem, it
suffices to identify and analyze the DADB sub-spectrum, which corresponds to a trivial AB system.
Red arrows  mark those four lines from DADB sub-spectra in both examples from CF3-CCl=CClF
given above. Perform the routine AB analysis to find νA, νB, JAB. All the other lines in the AB3
spectrum belong to DAQB which corresponds formally to a 2-spin system with IA = 1/2 and IB = 3/2.
General Remarks on Composite Particles
A composite particle of n spins with I = ½ has a maximum Fmax = n/2.
Particles will have individual F values ranging from
Fmin = 0 to Fmax in n/2 steps if n = even

Fmin = 1/2 to Fmax in (n+1)/2 steps if n = uneven
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The statistical weight of each particle with F is given by:
(2F + 1) ⋅ n!
[1] g(F,n) =
n n
( − F)!⋅ ( + F + 1)!
2 2
For details see the specific chapter on composite particles in Part II of this manuscript.
The AB3 spectrum consists of 16 lines, 4 from DADB and 12 from DAQB. Enumerate the 4 lines from
DADB with ν1 to ν4 from left to right (high frequency to low frequency) and evaluate parameters
following:
[2] So = ν1 − ν 4
[3] Si =ν 2 −ν3
[4] ∆ AB= S o ⋅ Si
ν +ν +ν +ν
[5] νC =1 2 3 4
4
∆
[6] ν A =νC + AB
2
∆
[7] νB =νC − AB
2
S −S
[8] J AB = o i
2
[9] JAB =ν1 −ν 2 =ν3 −ν 4
A repeated spacing in DADB is:
[10] C =ν1 − ν 3 =ν 2 + ν 4 = ∆ 2AB + J2AB
Remember: Only absolute values for ∆AB and JAB are obtained.
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It is not necessary to evaluate all the 12 lines from DAQB. But in principle explicit equations can
be derived describing those transition frequencies and intensities. In practice it is more convenient
to use TopSpin / DAISY for optimizing AB2 and AB3 cases.
8.21.3 Further Practical Examples
31
P NMR spectra of ligand and coordination compounds P4O6[Ni(CO)3]n (n = 0 to 4) revealed B4,
AB3, A2B2, A3B, and A4 spin systems.
P
P O O
O O
acceptor group
P O P
P O P
A = [Ni(CO)3] A O A
O P
P O O
O O
A
B4 A4
P
O O
P O P
A O A
P
O O
A2B2
A
P
P O O
O O
P O P
P O P A O A
O P
P O O
O O
A
AB3 A3B
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Four-Spin Systems
P4O6[Ni(CO)3]n System δP(A) δP(B) ∆δP JAB

coord. l.p.
0 B4 113.0 - -
1 AB3 126.3 117.6 8.7 38.8
2 A2B2 130.3 120.0 10.3 36.7
3 A3B 132.6 120.2 12.4 34.8
4 A4 132.9 - - -
31
Simulated 80.96 MHz P NMR Spectra of Compounds P4O6[Ni(CO)3]n
132 128 124 120 116 112 132 128 124 120 116 112
(ppm) (ppm)
n = 0. B4 n = 4. A4
132 128 124 120 116

(ppm)
n = 2. A2B2
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Four-Spin Systems
132 128 124 120 116 112 132 128 124 120 116 112
(ppm) (ppm)
n = 1. AB3 n = 3. A3B
31
Figure 431 : Ligand and coordination compounds P4O6[Ni(CO)3]n (n = 0 to 4) revealed P NMR spectra of
B4, AB3, A2B2, A3B, and A4 type resp..
8.22 The A4 and Related Spin Systems No. 42 to No. 47
All the systems 42 to 47 give rise to singlets:
50 40 30 20 10 0 -10 -20 -30 -40 -50

[Hz]
Figure 432 : The singlet corresponding to spectral systems 42 to 47.
AAÁ´Á´´´ [[A]2]2 AAÁ´´2 A2A´2 AA´3 A4

42 43 44 45 46 47
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579
Four-Spin Systems
Practically relevant are cases 43 and 47:
[[A]2]2 A4
43 47
Cl
H P
H H O O
H H
12
C C C P O P
H H O
H H
H H P
Cl H O O
F P
O O
H1 H3 F F
12 P O P
12 12
C
Br C C B C C F F A O A
P
H2 H4 F F F O O
A = [Ni(CO)3]
Coupling constants inside those 4-spin systems are not available by standard 1D NMR techniques.
13
Using the C satellite method, e. g. for
H1 H3 H1 H3
13 12 13 13
Br C C Br Br C C Br
H2 H4 H2 H4
2 3
reveals the “hidden” coupling constants, here JHH, and JHH. Technique and examples will be
discussed in chapters on 5-spin ([AB]2X) and 6-spin ([[A]2X]2) systems.
13
The C satellite method does not help for the higher symmetric CH4 and CF4 cases. NMR
measurements in nematic phases will solve the problem. But this technique is beyond the scope of
this manuscript.
If you are interested to learn more about this powerful technique, then read:
a) P. Diehl and C. L. Khetrapal, “NMR Studies of Molecules Oriented in the Nematic Phase of
Liquid Crystals”. Chapter 1 from “NMR Basic Principles and Progress - Grundlagen und
Fortschritte” Vol. 1, p. 1-95. Editors P. Diehl, E. Fluck and R. Kosfeld. Springer Verlag Berlin,
Heidelberg, New York, 1969.
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Four-Spin Systems
b) A. D. Buckingham and K. A. McLauchlan; “High Resolution Nuclear Magnetic Resonance in

Partially Oriented Molecules”. Chapter 2 from “Progress in Nuclear Magnetic Resonance
Spectroscopy”, Vol. 2, p. 63-109 (1971). Editors: J. W. Emsley, J. Feeney and L. H. Sutcliffe.
Pergamon Press, Oxford, 1967.
c) An instructive example for the [[A]2]2 system in [F2CS]2 was described by R. C. Long, Jr. and J.
H. Goldstein; J. Chem. Phys. 54, 1563-1569.
In contrast to monomeric phosgene O=CCl2 thiophosgene forms a dimer:
1 F S F 2
C C
3 F S F 4
19
F NMR spectra of thiophosgene were measured at 84.66 MHz in an isotropic solution and in a
lyotropic liquid crystalline medium (in a nematic phase), to yield the following parameters:
Isotropic Lyotropic
Parameters
Solution Mesophase
δ1 = δ2 = δ3 = δ4 -21.63 ppm
Scalar Coupling
Constants
J12 = J34 5.17 Hz 5.29
J13 = J24 137.06 Hz 137.56
J14 = J23 31.91 Hz 32.34
Dipolar Coupling
Constants
D12 = D34 - Hz 56.70
D13 = D24 - Hz -478.50
D14 = D23 - Hz 16.93
Chemical shift δF measured at 84.66 MHz vs. ext. CF3CCl3.
Since all the fluorine spins are chemically equivalent with δ1 = δ2 = δ3 = δ4 this [[A]2]2 system in
19
isotropic solution gives rise to a singlet in F NMR.
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Four-Spin Systems
A more complex pattern is observed for the lyotropic nematic phase which looks similar to the
simulation shown in the next figure:
10 5 0 -5 -10
(ppm)
19
Figure 433 : Simulated F NMR spectrum of thiophosgene in a lyotropic nematic phase.
Certainly it is tempting to learn more about scalar coupling constants Jik and dipolar coupling
constants Dik obtained from NEMA NMR techniques.
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Book 2
Up to here, in Book 1, we have studied systematically the analysis of NMR spectra of

1- to 4-spin systems supported by practically relevant examples from chemistry, pharmacy,
physics, and other fields. In this advanced part, Book 2, we will look into systems holding more
than 4 spins, partially associated with more complicated molecular structures. Within this context it
seems practical to us to group our material according to well known classes of compounds thus
supporting the understanding of complicated spectra with chemically relevant NMR parameters.
Naranath Bhranthan (http://en.wikipedia.org/wiki/Naranath_Bhranthan)
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First Order Systems from Single Spins
9 First Order Systems from

Single Spins
Multiple First Order Spin Systems Consisting of n Single Spins I = ½
In previous chapters we have studied the simpler cases of first order spin systems AX, AMR and
n
AMRX. This series may be generalized to the n-spin situation ∑ A . In such situations n bands
i =1
i
are detected each symmetrically placed around ν consisting of

A i
2n−1 lines of equal intensity (if
all Jik are unequal zero and no degenerate lines occur). Hence a total of n ⋅ 2n−1 lines will be
i k
observed for this system. This rule holds if each pair of spins A and A is connected by a spectral
ν Ai − ν A k
relation rik = where rik >> 1 or rik << -1.
Jik
A heteronuclear example for a 5 spin case of AHKRX type was found in the
fluoro(hydrogencyanide)xenon(II) cation characterized as a hexafluoroarsenate salt
+ -
[HCNXeF] [AsF6] . NMR parameters are given below:
1 13 15 129 19
H C N Xe F
1 2 3 4 5
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Chemical Shifts [ppm]
Spin i Type δi Referenced vs.

1
1 H 4.70 (CH3)4Si
13 29
2 C 104.1 (CH3)4 Si
15 15
3 N -235.1 CH3 NO2
129 129
4 Xe -1552 XeOF4
19 19
5 F -198.7 C FCl3
Coupling Constants [Hz]
ik Type Jik
1
12 JCH 308
2
13 JNH 13
3
14 JXeH 24.7
4
15 JFH 2.6
1
23 JNC 22
2
24 JXeC 84
3
25 JFC 18
1
34 JXeN 471
2
35 JNF 23.9
1
45 JXeF 6161
Exercise: Simulate individual nuclear specific spectra. Note, that coupling constants span a range
of 3-4 orders of magnitude. Specific problem for simulation: digital resolution.
For details read: A. A. Emara and G. J. Schrobilgen, Inorg. Chem. 31, 1323-1332 (1992). This
interesting paper lists a series of Xenon-Fluorine compounds.
31
A Homonuclear 5 Spin Case of ABCDE to AHKRX Type Consisting of P Nuclei
Pentaphenylcyclopentaphosphine (C6H5P)5 reacts with chromiumhexacarbonyl Cr(CO)6 forming the
complex [Cr(CO)5 (C6H5P)5].
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X-Ray Structure of [Cr(CO)5 (C6H5P)5]. (H. Wunderlich, Düsseldorf, priv. comm.)
Cyclopentaphosphine skeleton
31 1
Corresponding NMR parameters were determined by iteration of the 81 MHz P{ H} NMR
spectrum by M. Engelhardt. (Exp.: sat. solution in C6D6. Synthesis: J. Fenske, Dissertation 1989,
Düsseldorf).
Chemical Shifts δP
δi [ppm]
1 42.066
2 3.830
3 -5.919
4 -17.342
5 -23.379
Jik [Hz]
12 -329.89
13 -280.19
14 7.44
15 9.83
23 -6.16
24 76.72
25 -153.84
34 -259.92
35 6.38
45 -196.10
Exercise: Show by simulation that this system approaches the AHKRX situation when using high
field NMR spectrometers. Specific problem for simulation: digital resolution, 4 small and 6 large
couplings visible in a total of 5 regions.
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1
Chloroprene - a Homonuclear 5-Spin System Consisting of H Nuclei
H Cl 2
C C H C C 4
H C C 1 C C
H H 3 5
1
The H NMR spectra of CH2=CCl-CH=CH2 are characterized by ABCDE to AHKRX systems. NMR
parameters are listed in the following table using the spin enumeration shown above.
1
H NMR Parameters of Chloroprene
Parameter Type Type

δi δ δ [ppm]
1 δH δA 4.925
2 δH δC 4.797
3 δH δE 3.822
4 δH δD 4.412
5 δH δB 4.905
n
Jik JHH J [Hz]
2
12 JHH(gem) JAC -1.07
4
13 JHH(cis) JAE -0.60
5
14 JHH(cis,cis) JAD 0.67
5
15 JHH(cis,trans) JAB 0.72
4
23 JHH(trans) JCE -0.18
5
24 JHH(trans,cis) JCD 0.61
5
25 JHH(trans,trans) JBC 1.42
3
34 JHH(trans) JDE 16.54
3
35 JHH(cis) JBE 10.51
2
45 JHH(gem) JBD 0.95
For details read: Spectral analysis by A. A. Bothner-By, R. K. Harris; J. Amer. Chem. Soc. 87,
3445-3450 (1965).
Exercise: Show by simulation that this system approaches the AHKRK situation when using high
field NMR spectrometers. Specific problem for simulation: digital resolution, 8 small and 2 large
couplings visible in a total of 5 regions.
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The Composite Particle Concept
10 The Composite Particle Concept
An ensemble of n spins of type I = ½ forms a group An .
If all spins inside the composite particle are isochronous
νi = νj for all i, j = 1 to n
and if all coupling constants to each of the external spins k are identical:
Jik = Jjk for all i, j = 1 to n and for all k,
then the n spins inside the group An are called magnetically equivalent.
An isolated group An is defined by
Jik = Jjk = 0 for all i, j = 1 to n and for all k.
Internal coupling constants Jij do not influence the spectral appearance of HR (high resolution)
NMR single resonance spectra in isotropic phases and in anisotropic / nematic phases (NEMA
NMR) as well. Hence the internal coupling constants are not accessible from those spectra.
Some comments on methods to approximate hidden internal coupling constants are given at the
end of this chapter.
The group An is characterized by the total spin M(An) following
M(An) = n I(A)
M(An) is integral, if n is even, but half integral, if n is uneven. The composite group An can be
broken down into a series of specific substates A - which are called composite particles - each
having an effective total spin F(A), a multiplicity m(A) and a statistical weight g(A).
Using the notation for composite particles A(n,k)
and
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589
if n = even k = 0 – n/2
if n = uneven... k = 0 – (n-1)/2
we can write
F(A(n,k)) = n/2-k
n! ⋅ (n − 2k + 1)
g(n,k) = Notation from CORIO
(n − k + 1)! ⋅ k!
or using
F(A(n,k)) = F = n/2-k
as:
n! ⋅ (2 ⋅ F + 1)
g= Notation from DIEHL, HARRIS, JONES
n n
( + F + 1)! ⋅ ( − F)!
2 2
The multiplicity of a composite particle A is given by:
m(A(n,k)) = 2 F(A(n,k)) + 1
An overview is printed in the following tables:
Total Spin F(A) of Composite Particles A of Groups An
n 1 2 3 4 5 6 7 8 9
M(An) 1/2 1 3/2 2 5/2 3 7/2 4 9/2
k
0 F(A) 1/2 1 3/2 2 5/2 3 7/2 4 9/2
1 F(A) 0 1/2 1 3/2 2 5/2 3 7/2
2 F(A) 0 1/2 1 3/2 2 5/2
3 F(A) 0 1/2 1 3/2
4 F(A) 0 1/2
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Statistical Weight g of Composite Particles A of Groups An
n 1 2 3 4 5 6 7 8 9
M(An) 1/2 1 3/2 2 5/2 3 7/2 4 9/2
k
0 g(A) 1 1 1 1 1 1 1 1 1
1 g(A) 1 2 3 4 5 6 7 8
2 g(A) 2 5 9 14 20 27
3 g(A) 5 14 28 48
4 g(A) 14 42
Multiplicity of Composite Particles A of Groups An
n 1 2 3 4 5 6 7 8 9
M(An) 1/2 1 3/2 2 5/2 3 7/2 4 9/2
k
0 m(A) 2 3 4 5 6 7 8 9 10
1 m(A) 1 2 3 4 5 6 7 8
2 m(A) 1 2 3 4 5 6
3 m(A) 1 2 3 4
4 m(A) 1 2
The standard spectroscopic symbols may be used for multiplicities like:
Spectroscopic Symbols for Composite Particles A of Groups An
n 1 2 3 4 5 6 7 8 9
M(An) 1/2 1 3/2 2 5/2 3 7/2 4 9/2
k
0 D T Q Qt Sx Sp Oc No Dc
1 m(A) S D T Q Qt Sx Sp Oc
2 m(A) S D T Q Qt Sx
3 m(A) S D T Q
4 m(A) S D
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10.1 Spectra of Isolated Composite Particles
Each isolated An group gives rise to a singlet centered at the frequency νA showing a spectral
intensity proportional to n ⋅ 2n−1 .
This singlet is a superposition of
n/2 if n = even, or
n/2 + 1/2 if n = odd
individual sub-spectra (singlets) derived from all possible composite particles of type A(n,k).
Each A(n,k) contributes a spectral intensity of
2 n n
int(A(n,k)) = ⋅ ( − k) ⋅ ( − k + 1) ⋅ (n − 2 ⋅ k + 1) Notation from CORIO
3 2 2
or using
F(A(n,k)) = F = n/2-k
2
int(A(n,k)) = ⋅ F ⋅ (F + 1) ⋅ (2 ⋅ F + 1) Notation from DIEHL, HARRIS, JONES
3
Hence the total spectrum of the An group will be formed by the superposition of all int(A(n,k)
weighted by corresponding g(n,k) to yield a total intensity of intT(An):
n
=
int T (An) ∑ A (n,k) ⋅ g(n,k)
k =0
n
2 n n n!
int T (A=
n) ∑ 3 ⋅( 2 − k) ⋅( 2 − k + 1) ⋅(n − 2 ⋅k + 1)2 ⋅ (n − k + 1)!⋅k!
k =0
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592
rewritten as:
2 n!
=
int T (An) ∑ 3 ⋅F ⋅(F + 1) ⋅(2 ⋅F + 1)2 ⋅ n n
F ( + F + 1)! ⋅ ( − F)!
2 2
The latter expressions are simplified to:
int T (An) = n ⋅ 2n−1
10.1.1 Example 1: The A2 Group
The A2 group may be handled as sum of 1 A(2,0) + 1 A(2,1) composite particles. with F(A(2,0) =
1 and F(A(2,1) = 0. Hence one singlet is expected at νA with an intensity of 4*1+0*1 = 4.
T S
mT = -1
mT = 0
mT = +1
1 1
The A3 group may be dealt with as sum of 1 A(3,0) + 2 A(3,1) composite particles with
F(A(3,0) = 3/2 and F(A(3,1) = 1/2. Hence one singlet is expected at νA with an intensity of
10*1+1*2 = 12.
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593
Q D
mT = -3/2
mT = -1/2
mT = +1/2
mT = +3/2
1 2
The A4 group may be handled as the sum of 1 A(4,0) + 3 A(4,1) + 2 A(4,2) composite particles.
with F(A(4,0) = 2, F(A(4,1) = 1 and F(A(4,2) = 0. Hence one singlet is expected at νA with an
intensity of 20*1+4*3+0*2 = 32.
Qt T S
mT = +2
mT = -1
mT = 0
mT = +1
mT = -2
1 3 2
Spectra of Coupled Composite Particles
The powerful concept of composite particle theory allows for a simplified description of NMR
spectra. For didactical purposes the single spin A is handled as the primitive group An with n = 1.
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Examples for Practical Problems – I
System Examples
AX2 CHClF2, CH2ClF
AX3 CHF3, CH3F, CH3PCl2
13 -
AX4 CF4, SiF4, [PF4] (h.t.)
-
AX6 (CH3)2CFCl, (CF3)2CHCl, [PF6]
AX9 (CH3)3CF, (CH3)3CPCl2, (CH3O)3P
AX18 [(CH3)3C]2PCl, [(CH3)3C]2P(S)Cl
A2X2 CH2F2
A2X3 CH3CF2Cl, CF3CH2Cl
A3X3 CH3CF3
AB2 2,6-C5H3NCl2, 1,2,3-C6H3Cl3
AB3 CH3SH, CH3CHR2, CH3CHRR´
AB4 SF5Cl
AB6 (CH3)2CHR
A2B2 SF4 (l.t.)*, one isomer of c-C4H4(C6H5)2(COOH)2
A2B3 CH3CH2R
A3B3 (CH3)2CRR´*
*) l.t.: at low temperature, frozen conformer.
Examples for Practical Problems - II
System Examples
ABX2 CHCl=CH-CF2Cl, CFCl=CF-CF2Cl
ABX3 CHCl=CH-CF3, CFCl=CF-CF3, CH3CH2OR*
ABC2 CHCl=CH-CH2Cl
ABC3 CHCl=CH-CH3, CH3CH2OR*
AB2X C6H3Cl2F
AB3X CH3CHClF, CH3CHClP(O)((OR)2
AB4X WF5OR
-
A2B2X [PF4] (l.t.), R2NPF4 (l.t.)
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Examples for Practical Problems - III
System Examples
ABCX2 CH2=CH-CF2Cl, CF2=CF-CF2Cl
ABCX3 CH2=CH-CF3, CF2=CF-CF3
ABCD2 CH2=CH-CH2Cl
ABCD3 CH2=CH-CH3
To understand the importance of composite particle theory we will study in detail the AX n and ABn
spin systems for n = 2 - 4 in specific chapters of this manuscript.
Some Comments on Hidden Couplings in Composite Particles
There is a convenient way in approximating the hidden internal coupling constants: reduction of
symmetry in composite particles by isotopic substitution: e.g. CH2Cl2 and CHDCl2.
12 1
The A2 composite particle in CH2Cl2 gives rise to a singlet in standard H NMR spectra.
12 1/2 1
But CHDCl2 clearly shows the AX pattern of an A X spin system including the 1:1:1 triplet in the
1 2 2
A-region ( H) and the 1:1 doublet for the X nucleus (D = H). A coupling constant JDH is resolved
obeying the general relation:
JHH γH
= = 6.5144
JDH γD
Since γH and γD are well known constants and JDH is accessible by experiment JHH is calculated.
1/2 1
Since the first order analysis of A X leads to the absolute value of JDH, only the absolute value of
is JHH accessible.
There is another, less convenient, way in approximating the hidden internal coupling constants:
reduction of symmetry in composite particles by isotopic substitution, not by deuterium but by
3
tritium H.
This radioactive isotope of hydrogen requires special techniques. Tritium is characterized by spin I
= ½ and is the nucleus with the highest resonance frequency (106.6640 MHz), higher than that of
protons (100.0000 MHz).
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12 1/2 1/2
The tritium spectrum of a - CHT- unit shows the AX pattern of a standard A X spin system
1 3
including the 1:1 doublet in the A-region ( H) and the 1:1 doublet for the X nucleus (T = H). Thus a
2
coupling constant JTH is resolved obeying the general relation:
JHH γH
= = 0.9372
JTH γ T
Since γH and γT are well known constants and JTH is obtained by H NMR experiment, JHH is
3
accessible, but with one restriction, like in the previous case, as absolute value of JHH.
AL-RAWI, ELVIDGE, AND JONES (J. Chem. Soc. Perkin II, 1975, 449-452) applied the tritium
2 2
technique to obtain JTH and JHH in methylene and methyl fragments.
Examples:
2 2
Absolute Values of JTH and JHH in [Hz]
2 2
Compounds JTH JHH
CH2(COOEt)2 16.84 15.79
CH3NO2 13.69 12.84
CH3COONa 14.94 14.02
CH3CN 17.15 16.08
The hidden signs of geminal coupling constants in CH2 groups may be deduced from Double
Resonance studies on three spin systems like ABC or ABX in RCH2-CHR´R´´, RCH2-CFR´R´´,
FCH2-CRR´R´´ or RCH2-P(O)R´R´´ etc.. Those cases are discussed in specific chapters in book 1
of this manuscript.
2
Note: Sign of JHH is negative for aliphatic CH2 and CH3 groups.
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10.2 Composite Particles AB4 and A4B
AB4 and A4B Spectra from Pentafluorosulphanyl Compounds SF5R
SF6 gives rise to an A6 singlet line at δF = -56 ppm. Mono-substituted derivatives SF5R form the
19
class of pentafluorosulphanyl compounds, corresponding to AB4 or A4B spin systems in F NMR.
The hexa-coordinated skeleton in SF5R is stationary, no dynamic exchange is observed.
F B A Feq
F B A Feq
F S R A S R B S R Fax S R
F B A Feq
F B A Feq
SF5R AB4 A 4B
NMR parameters from two examples are listed below, using the characteristic parameter,
∆ = δFax - δFeq, the difference in chemical shifts between axial and equatorial fluorines:
δFax δFeq ∆
2
R JFaxFeq Spin
[ppm] [ppm] [Hz] [ppm] System
Cl -62.3 -125.2 150 62.9 AB4 - AX4
OPh -72.7 -62.6 158.5 -10.1 A4B
Data from: R. K. Harris, K. J. Packer; J. Chem. Soc. 1961, 4736-4740.
Expanding the ideas of composite particle theory discussed in preceding chapters, the AB4
spectrum may be described as a superposition of three sub-spectra corresponding to DS, DT and
DQt. Transition frequencies and intensities for all 25 lines can be expressed algebraically. The DS
state yields one characteristic line only which is located at νA. νB and the absolute value of JAB are
obtained from analysis of the DT sub-spectrum.
An analogous treatment is valid for the inverse problem in A4B.
19
Exercise: Simulate F NMR spectra for SF5Cl. This AB4 case is weakly coupled approximating the
AX4 case for higher fields.
More complex structure exhibits the A4B case of SF5OPh.
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-62 -64 -66 -68 -70 -72 -74 -76

(ppm)
F NMR spectrum of SF5OPh. A4B system. Red arrow: δF(B).

19
Figure 434 : Simulated 94.1 MHz
In favorable cases manual analysis of AB4 spectra is possible, but it is more convenient and time
saving to use the line shape analytical method of TopSpin / DAISY to determine the relevant
parameters: resonance frequencies νA, νB, coupling constant JAB and spectral half widths resp.
AB4X and A4BX Systems are Observed for SF5R where R = OSO2F and R = OF:
O O
F B F A
F S B F A
F S O F A X F S O B X
F B F F A
F B F A
SF5OSO2F AB4X SF5OF A4BX
a) b)
SF5OSO2F SF5OF
δF Type Data Type Data
Fax A -55.6 [ppm] B -55.6
Feq B4 -71.9 [ppm] A4 -53.8
OSO2F X -45.1 [ppm] X -188.8
JFF Type Data
2
JFF AB 156 [Hz] AB 155
4
JFFax AX 0.9 [Hz] BX 0.6
4
JFFeq BX 9.2 [Hz] AX 18.3
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Data from:
R. K. Harris, K. J. Packer; a) J. Chem. Soc. 1961, 4736-4740. b) ibid. 1962, 3077-3082.
Exercise: Simulate AB4X and A4BX spectra.
A complex [AB4]2 multiplet structure is observed for SF5-SF5
FB FB´
FB FB´
FA S S FA´
FB FB´
FB FB´
NMR Data from SF5-SF5
Parameter Type Data

∆ *) 3.72 [ppm]
2
JFaxFeq AB ± 137.9 [Hz]
3
JFaxFeq´ AB´  5.1 [Hz]
3
JFaxFax´ AA´  0.5 [Hz]
3
JFeqFeq´ BB´  51.3 [Hz]
)
* ∆ = δF(Fax)-δF(Feq)
If you are interested to learn more about this complex problem, then read:
E. G. Finer, R. K. Harris; Spectro. Chim. Acta 24A, 1939-1950 (1968).
19
Finer and Harris solved this [AB4]2 problem using F NMR spectra at 94.1 MHz. Simulate
19
corresponding F NMR spectra (which are complex even when using supercon magnets at highest
fields)!
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10.3 Composite Particles A2B3 / A2X3 and A3B2 / A3X2

– Analysis of A2B3 Spectra
10.3.1 The A2B3 Spectrum from [NiL5] [BF4]2 – 31P{1H} at Low Temperatures
2+ 2+
Ni and phosphite ligands L form stable cationic complexes [NiL5] which may be isolated as salts
of monovalent anions, e. g. [NiL5] [BF4]2. At room temperature a singlet is observed in
↔ [NiL4]
31 1 2+ 2+
36.43 MHz P{ H} NMR spectra indicating a dynamic exchange [NiL5] + L. Cooling
solutions in CHClF2 /CD2Cl2 (9:1) to -123°C slows down this dynamic exchange where
31 1
P{ H} NMR reveals a “frozen” trigonal-bipyramidal structure characterized by an A2B3 spin
system.
L Pax A O C
L Peq B
L Ni Peq Ni B Ni L = P(OCH2)3CCH3 P O C C C
L Peq B
L Pax A O C
31 1
The following experimental data for proton decoupled 36.4324 MHz P{ H} NMR were found:
Parameter Data
δP(A2) 119.0 ppm
δP(B3) 103.6 ppm

JAB 121 Hz
and used to simulate subsequent spectra using parameters:
νP(A2) 4335.452 Hz
νP(B3) 3774.393 Hz
JAB 121 Hz
HWB 1 Hz
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The modified spectral relation r for this system is -4.637 where r is defined by:
νP (Peq ) −νP (Pax )

r=
JPP (PeqPax )
A2B3 Spectrum
4400 4200 4000 3800 3600

(Hz)
A2 part B3 part
31 1
Figure 435 : Simulated 36.4324 MHz P{ H} NMR spectrum of [NiL5] [BF4]2 in CHClF2 / CD2Cl2 (9:1) at
-123°C.
Analysis of the A2B3 Spectrum
The A2B3 spin system gives rise to a total of 37 lines, where 9 lines are too weak to be observed
and four lines are degenerated summing up to a significant strong line centered at νB. Hence 25
lines remain, 12 lines in the A2 part, a strong line centered at νB, and additional 12 lines in the B3
part.
Lines Number Intensity

LINES CALCULATED 37 80.000
LINES SUPPRESSED by MINIMUM INTENSITY (Amin = 0.010) 9 0.019
LINES BEFORE DEGENERACY 28 79.981
LINES AFTER DEGENERACY 25 79.981
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In practice we see 25 lines – but we will only need 12 lines for spectral analysis:
A2B3 Spectrum
Figure 436 : The A2 part
Figure 437 : The B3 part
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Those 12 relevant lines are indicated in the following table:
Number Frequency Intensity Used for Frequency

Left to Right Calculated Calculated Analysis Peak Picking
1 4550.4767 0.9944 a3 4550.47
2 4512.7534 1.1532 4512.75
3 4454.5725 1.2348 4454.57
4 4416.1909 1.4652 4416.19
5 4410.1726 3.0313 a6 4410.17
6 4393.2939 3.2842 a4 4393.29
7 4338.1431 1.7409 4338.14
8 4306.7664 2.0602 4306.76
9 4286.5146 4.7149 a2 4286.51
10 4277.6101 4.9678 a5 4277.61
11 4194.5356 3.3178 4194.53
12 4167.4723 4.0343 a1 4167.47
13 3895.7110 5.0307 3895.71
14 3881.1724 2.9687 b5 3881.17
15 3874.4958 5.7706 3874.49
16 3861.8683 4.0056 b3 3861.87
17 3774.3930 12.0000 b6 3774.40
18 3765.9641 2.8392 3765.97
19 3758.0664 3.6007 3758.07
20 3748.6098 1.7471 b4 3748.61
21 3725.0402 2.2821 3725.04
22 3669.4016 2.1527 3669.40
23 3648.6419 2.6176 3648.64
24 3641.8304 1.2851 b2 3641.84
25 3612.8094 1.6822 b1 3612.81
Remember: The strong line centered at b6 corresponds directly to νB(B3).
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The analysis of A2B3 spectra uses the following auxiliary parameters:
Auxiliary Parameters
∆ AB =ν A −νB
1 1
R1 = ( ∆ AB − JAB )2 + 6 J2AB R2 = ( ∆ AB + JAB )2 + 6 J2AB
2 2
1 1
R3 = ( ∆ AB + JAB )2 + 2J2AB R 4 = ( ∆ AB − JAB )2 + 2J2AB
2 2
and from:
Explicit Expressions for 12 Transition Frequencies
Lines a1 to a6 Contribute Lines b1 to b6 Contribute
to the A2 Part to the B3 Part
1 5 1 5
a1 =ν A − ( ∆ AB + JAB − R1 ) b1 =ν A − ( ∆ AB + JAB + R1 )
2 2 2 2
1 3 1 3
a2 =ν A − ( ∆ AB + JAB − R3 ) b2 =ν A − ( ∆ AB + JAB + R3 )
2 2 2 2
1 5 1 5
a3 =ν A − ( ∆ AB − JAB − R2 ) b3 =ν A − ( ∆ AB − JAB + R2 )
2 2 2 2
1 1
a4 =ν A − (R 4 − R3 ) b4 =ν A − (R3 + R 4 )
2 2
1 1 3
a5 =ν A − (R3 − R 4 ) b5 =ν A − ( ∆ AB − JAB + R 4 )
2 2 2
1 3
a6 =ν A − ( ∆ AB − JAB − R 4 ) b6 =ν A − ∆ AB =νB
2 2
are derived:
6 Equations for the Analysis of A2B3 Spectra
1 1
ν=
A (a4 + a5 ) ∆ AB= (a4 + a5 ) − b2
2 2
1
νB =b6 JAB= [(a6 − a2 ) + (b5 − b2 )]
3
1
νB = b 2 + b5 − b 4 JAB= [(a3 − a1 ) + (b3 − b1 )]
5
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31 1
Applying rules shown above to the 36.4324 MHz P{ H} NMR spectrum of [NiL5] [BF4]2 yields
parameters given in [Hz]:
Equations Results Equations Results

1 1
ν=
A (a4 + a5 ) 4335.45 ∆ AB= (a4 + a5 ) − b2 561.05
2 2
1
νB =b6 3774.40 JAB= [(a6 − a2 ) + (b5 − b2 )] 120.997
3
1
νB = b 2 + b5 − b 4 3774.40 JAB= [(a3 − a1 ) + (b3 − b1 )] 121.000
5
Hence, the manual analysis of A2B3 spectra leads to the parameters wanted: νA, νB, JAB.
But do we really need to follow the algebraic equations by manual analysis?
TopSpin / DAISY allows for the convenient, semi-automated line shape analysis. Starting off with
an educated guess for νA, νB, JAB and the spectral half widths for the A- and B-lines rapidly leads to
convergence and the optimized NMR parameters. An educated guess may be found conveniently
by comparative inspection of your own systematic series of simulated spectra (use your TopSpin /
DAISY).
Spectral moments proofed to be useful tools to determine chemical shifts in ABC spectra. This
technique may be applied to A2B3 cases as well.
The first spectral moment M1 of an A2B3 spectrum is given by:
nl
∑ ν ⋅I
i =1
i i
1
[1] M=1 nl
= (2 ν A + 3 νB )
5
∑I i =1
i
where νi and Ii correspond to transition frequencies and transition intensities.
M1 solely depends on resonance frequencies νA and νB. M1 is independent of the coupling constant
JAB (and hence independent of rAB). This yields another approach to resonance frequency νA:
1
[2] =
νA (5M1 − 3 νB )
2
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which may be used as a starting parameter for iterations of more complex A2B3 spectra. The
resonance frequency νB is easily extracted as strong line b6 as described above.
Comparison of A2B3 and A3B2 Spectra
For didactical purposes we will use a modified spectral relation r
νP (Peq ) − νP (Peq )
r=
JPP (PeqPax )
to characterize spectra from trigonal-bipyramidal complexes of general type [ML5].
2+
[NiL5] (L = P(OCH2)3CCH3) shown above is characterized by an A2B3 system with r = -4.637. For
2+
[PdL5] (L = P(OCH3)3) an A3B2 system with r = +7.372 is found and shown below. A pair of
spectra with +r and -r values (identical absolute values of r) will appear as mirror images to each
other.
The analysis of A3B2 spectra follows rules analogous to those shown above for A2B3.
A3B2 Spectrum
4100 4000 3900 3800 3700 3600

(Hz)
31 1
Figure 438 : 36.4324 MHz P{ H} NMR spectrum of [PdL5][BPh4]2 (L = P(OCH2)3CCH3) in CHClF2 /
CD2Cl2 (9:1) at -157°C
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10.3.2 Rhodium Complexes [RhL5][BPh4] form A3B2X or A2B3X Systems
31 1
A 36.43 MHz P{ H} NMR spectrum at -134°C of [RhL5][BPh4] (L = P(OCH3)3) reveals a typical
A3B2X pattern which confirms the “frozen” trigonal-bipyramidal structure. Equatorial phosphorus
atoms form the A3 while the axial phosphorous atoms give rise to the B2 composite particles. X is
103
due to Rh which occurs as a 100% spin I = ½ element.
5400 5200 5000 4800 4600

(Hz)
31 1
Figure 439 : Simulated 36.43 MHz P{ H} NMR spectrum of [RhL5][BPh4] (L = P(OCH3)3) in CHClF2 /
CD2Cl2 (9:1) at -134°C. A3B2 part of A3B2X with r = (νPeq-νPax) / JPP = + 5.88
NMR Data for [RhL5][BPh4] (L = P(OCH3)3)
Parameter Type Type Data

δ1 A3 Peq 144.1 ppm
δ2 B2 Pax 129.4 ppm
δ3 X Rh 0 by def. ppm
ν1 A3 Peq 5249.91 Hz
ν2 B2 Pax 4714.35 Hz
ν3 X Rh 0 by def. Hz
2
J12 AB JPP(PaxPeq) 68 Hz
1
J13 AX JRhP(RhPeq) 206 Hz
1
J23 BX JRhP(RhPax) 143 Hz
HWB 5 by def. Hz
Data from: P. Meakin, J. P. Jesson; J. Amer. Chem. Soc. 96, 5760-5774 (1974)
Dynamical exchange increases with increasing temperature following a Berry Pseudo Rotation
(BPR) mechanism typical for trigonal-bi-pyramidal structures. Rh-P bonds are preserved during
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608
BPR exchange. At -65°C a simple doublet is observed explained by: A3B2X↔ C5X. Parameters are
expected: δC = (3δA+2δB)/5 and JCX = (3JAX+2JBX)/5.
5400 5200 5000 4800 4600

(Hz)
31 1
Figure 440 : Simulated 36.43 MHz P{ H} NMR spectrum of [RhL5][BPh4] (L = P(OCH3)3) at -65°C. C5
part of C5X
Further warming up leads to line broadening resulting in the collapse of the doublet and finally at
+82°C to a neat singlet signal. This observation is explained by a dissociative mechanism
following: [RhL5] ↔ [RhL4] + L , where Rh-P bonds and couplings are lost.
+ +
103
Rh spectra of [RhL5][BPh4] (L = P(OCH3)3) were not described in the literature cited above. From
a didactical point of view it seems justified to speculate about the X parts of A3B2X and C5X
systems. For A3B2X a triplet of quartets is calculated indicating the couplings JAX and JBX
separately. For C5X a simple sextet results where an averaged coupling JCX follows:
JCX = (3JAX+2JBX)/5.
Hence the distances of outer lines in both spectra should be identical (if intrinsic couplings JAX and
JBX do not depend on temperature).
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400 200 0 -200 -400
400 200 0 -200 -400

(Hz)
103 1
Figure 441 : Hypothetical 2.8664 MHz Rh{ H} NMR spectra of [RhL5][BPh4] (L = P(OCH3)3). Upper: at
-134°C. Lower: at -65°C. νRh is arbitrarily centered at 0 Hz
A2B3X from [RhL5][BPh4] (L = P(OCH2)3CCH3) in CHClF2/CD2Cl2 (9:1) at -127°C
An analogous Rhodium complex was prepared using a caged phosphite P(CH2O)3CCH3 as ligand
L in [RhL5][BPh4] which gives rise to an A2B3X system where the A2B3 skeleton is characterized by
r = - 5.56.
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A2B3X from [RhL5][BPh4] (L = P(OCH2)3CCH3) in CHClF2/CD2Cl2 (9:1) at -127°C

δ1 A2 Pax 125.6 ppm
δ2 B3 Peq 115.0 ppm
δ3 X Rh 0 by def. ppm
ν1 A2 Pax 4575.91 Hz
ν2 B3 Peq 4189.73 Hz
ν3 X Rh 0 by def. Hz
2
J12 AB JPP(PaxPeq) 69.5 Hz
1
J13 BX JRhP(RhPeq) 208 Hz
1
J23 AX JRhP(RhPax) 140 Hz
HWB 5 by def. Hz
Data from: P. Meakin, J. P. Jesson; J. Amer. Chem. Soc. 96, 5760-5774 (1974)
4800 4600 4400 4200 4000

(Hz)
Figure 442 : A2B3X from [RhL5][BPh4] (L = P(OCH2)3CCH3) in CHClF2 / CD2Cl2 (9:1) at -127°C
Exercise: Simulate spectrum and sub-spectra. Try your hand to analyze this spectrum.
Suggested Readings
MEAKIN and JESSON expanded studies on neutral and cationic metal phosphite complexes [ML5]
1+ 2+
(Fe, Ru, Os), [ML5] (Co, Rh, Ir) and [ML5] (Ni, Pd, Pt) which are of intrinsic interest to NMR
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611
spectroscopists. The influence of metal and ligand types, solvent and temperature effects are
discussed and principles of Dynamic NMR as well.
For details read the papers from the P. MEAKIN and J. P. JESSON group:
a) Nucl. Chem. Letters 9, 1221-1224 (1973);
b) J. Amer. Chem. Soc. 94, 1344-1346 (1973);
c) ibid. 95, 7272-7281 (1974);
d) ibid. 96, 5760-5774 (1974);
e) ibid. 97, 1254-1255 (1975);
f) ibid. 99, 117-120 (1977).
But pay attention: The authors used two different definitions for chemical shifts δP in their papers.
We decided to set δP(P(OCH3)3) = 140.4 ppm vs. 85% H3PO4 and simplify the above given tables
according to IUPAC standard definitions: Chemical shifts δP [ppm] are indirectly referenced vs.
85% H3PO4 and are positive for downfield signals. Note: Left is positive, right is negative.
Increasing the Field Strength Simplifies the Spectral Pattern
31 1
A 202.4 MHz P{ H} NMR simulation for [RhL5][BPh4] (L = P(OCH2)3CCH3) in CHClF2 / CD2Cl2
(9:1) at -127°C yields a “sextet” which corresponds to a doublet of quartets for the axial and a
doublet of triplets for the equatorial phosphorous atoms. This A2B3X approximates the A2M3X
situation.
25600 25200 24800 24400 24000 23600 23200

(Hz)
31 1
Figure 443 : Simulated 202.4 MHz P{ H} NMR spectrum of [RhL5][BPh4] (L = P(OCH2)3CCH3) in
CHClF2 / CD2Cl2 (9:1) at -127°C.
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This “sextet” with relative intensities around 1:3:4:4:3:1 indicates that JAX : JAB ≈ ± 2. A strikingly
1
similar pattern is found for the 500 MHz H NMR spectrum of CH3CH2P(O)Cl2 which will be
discussed in a subsequent chapter on spectral properties of A2B3 systems from ethyl compounds.
Finally a Tricky Exercise on Platinum Complexes [PtL5]2+
195
Natural platinum consists of 33.8 % Pt with I = ½ while 66.2% is spin-inactive (several isotopes).
31 1
Low temperature 36.43 MHz P {H} NMR spectra of [PtL5][BPh4]2 show over-lapping A3B2X and
A3B2 systems where A3 = 3 Peq and B2 = 2 Pax .
31 1 2+
Simulate and reanalyze the low-temperature P{ H} NMR spectra of [PtL5] [BPh4]2.
Data are listed below.
31 1 2+
Data from P{ H} NMR Spectra of [PtL5] [BPh4]2
Fragment Ligand L
A3B2X P(OCH3)3 P(OCH2)3CCH3
Parameter Type Data Data
δ1 A3 81.4 68.4
δ2 B2 60.6 65.0
δ3 X - -
ν1 A3 2980.17 2491.98
ν2 B2 2207.80 2368.11
ν3 X - -
J12 JAB 52.5 52
J13 JAX 4100 4123
J23 JBX 2840 2744
A3B2
ν1 A3 2980.17 2491.98
ν2 B2 2207.80 2368.11
J12 JAB 52.5 52
HWB 5 by def 5 by def.
Simulate the total spectrum as the sum of two overlapping fragments A2B3X and A2B3. Note that
several sub-spectra of type a2b3 and a3b2 are observed, which are characterized by effective
spectral relations reff.
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Study subsequent spectra and calculate reff following:
νPeq − νPax JPtPeq − JPtPex

=
reff − mPt ⋅
JAB JAB
5000 4500 4000 3500 3000 2500 2000 1500 1000 500
(Hz)
31 1
Figure 444 : 36.43 MHz P {H} NMR spectrum of [PtL5][BPh4]2 (L = P(OCH3)3) at -140°C.
4500 4000 3500 3000 2500 2000 1500 1000 500

(Hz)
31 1
Figure 445 : 36.43 MHz P {H} NMR spectrum of [PtL5][BPh4]2 (L = P(OCH2)3CCH3) at
-135°C
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Five Spins: CH3CH2R – A2B3 – A2M3 – ABC3 – ABM3
11 Five Spins: CH3CH2R – A2B3, A2M3,

ABC3, ABM3 Systems
11.1 A2B3 and A2X3 Spectra from Ethyl Compounds CH3CH2-R
In the early days of NMR when spectrometers ran at 60 MHz, accurate studies characterized the
A2B3 type spectra of ethyl compounds like:
δH(CH2) δH(CH3) ∆δ
3
R JHH
δH(A2) δH(B3) δH(A2)-δH(B3) JAB

C(CH2CH3)3 1.1709 0.7276 0.4433 7.528
N(CH2CH3)2 2.4253 0.9697 1.4556 7.127
O(CH2CH3) 3.3692 1.1361 2.2331 6.973
I 3.1546 1.8593 1.2953 7.446
Br 3.3662 1.6767 1.6895 7.327
Cl 3.5053 1.4882 2.0171 7.232
S. Ebersole, S. Castellano, A. A. Bothner-By; J. Phys. Chem. 68, 3430-3431 (1964)
With increasing electronegativity of substituents R in ethyl compounds C2H5R the spectral relation r
= (νH(CH2)-νH(CH3))/ JHH increases and patterns of corresponding A2B3 spectra approximate A2X3.
3
Ethylchloride will exhibit a neat A2X3 at 200 MHz, while ethyliodide will need the high field of a 400
MHz spectrometer to simplify to the A2X3 pattern. Hence modern high field NMR spectrometers will
show many ethyl spectra as simple A2X3 cases. A quartet (2H) at δH(A2) and a triplet (3H) at δH(X3)
are observed with 5 repeated spacings corresponding to JAB.
It is much more exciting to study the basic A2B3 spectra available from ethyl compounds at lower
fields or from chemically different model systems e. g. penta-coordinated metal complexes [ML]5
with trigonal-bipyramidal structures as described in a preceding chapter of this manuscript.
1
H NMR spectra of ethylpropionate CH3CH3COOCH2CH3 reveal two individual sets of A2B3
systems at 200 MHz which will approximate A2X3 spectra at 500 MHz.
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1
Figure 446 : 200 MHz H NMR spectrum of Ethylpropionate
1
200 MHz H NMR Data of Ethylpropionate and Ethylbenzoate
νH(CH2) νH(CH3)
3
JHH HWB
νH(A2) νH(B3) JAB Global

CH3-CH2-COO-CH2-CH3 462.4404 227.8165 7.5896 1.2963
CH3-CH2-COO-CH2-CH3 825.0458 251.9707 7.1457 1.3036
C6H5-COO-CH2-CH3 864.3628 276.0387 7.1193 0.6197
1
H NMR spectra of propionic acid and the corresponding propionate anion represent first order
systems of A2X3- type at 500 MHz while A2B3 will appear at 100 MHz. Chemical shifts δH and
3
coupling constants JHH were determined using a 0.1 m solution in D2O.
- H+
CH3 CH2 COOH CH3 CH2 COO-
+
+H
∆i
-
HL L
δH CH2 2.4006 2.1669 +0.2337 [ppm]
δH CH3 1.0968 1.0402 +0.0466 [ppm]

3
JHH CH3-CH2 7.54 7.68 -0.14 [Hz]
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Non-equivalence Effects in Methylene Protons
Example: Diethylacetal
A pair of ethoxy groups attached to a prochiral center exhibits isochronous methyl groups and an
anisochronous pair of protons inside a methylene group. ABC3 to ABX3 spectra are observed. This
phenomenon was termed “non-equivalence effect” in the early days of NMR spectroscopy.
Instructive examples were found in diethylacetals RRĆ(OC2H5)2 , e.g. in:
H H H
H 3C C O C O C CH3
H CH3 H
1
A simulated 200 MHz H NMR spectrum of this compound is shown below:
1
Figure 447 : Simulated 200 MHz H NMR spectrum of diethylacetal.
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617
It consists of two fragments:
a) Fragment 1: the CH3CH unit which shows AX3 character and

b) Fragment 2: the C(OCH2CH3)2 unit giving rise to the typical ABX3 pattern.
720 710 700 690 680 670

(Hz)
Figure 448 : Expansion for fragment 2: AB part of C(OCH2CH3)2
1
200 MHz H NMR Spectrum of Diethylacetal
CH3CH(OCH2CH3)2
ν1 A 709.600
ν2 B 679.540
ν3 X3 223.90
J12 JAB -9.427
J13 JAX 7.043
J23 JBX 7.043
CH3CH(OCH2CH3)2
ν1 A 935.140
ν2 X3 259.440
J12 JAX 5.300
For details read: L. S. Rattet, J. H. Goldstein; Org. Magn. Res. 1, 229-237 (1969)
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Analogous non-equivalence effects were observed for diethylsulphite:
H O H
H 3C C O S O C CH3
H H
Non-equivalence Effects in Chiral Compounds
If an ethyl group is affiliated with a chiral center, e. g.
R1 H R1 H R1 O H
R2 C C CH3 R2 C O C CH3 R2 C C O C CH3
R3 H R3 H R3 H
(R ≠ R ≠ R ), then non-equivalence effects in ABC3 to ABX3 spectra are observed.

1 2 3
1 2
If malonic acid diethylesters are substituted by chiral groups R or R in
H O R1 O H
H 3C C O C C C O C CH3
H R2 H
then a two-fold non-equivalence occurs. Both ethyl groups are non-equivalent and the pair of
methylene protons in each methylene group is non-equivalent. Hence the superposition of two
different ABC3 or at higher field ABX3 spectra is observed.
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11.2 Ethyl Groups Attached to Spin Active Units
Ethylformiate CH3CH2OOCH
The single formic proton OOCH resonates at 8.021 ppm and is responsible for small long range
4 5
couplings to methylene protons JHH = -0.83 Hz and to methyl protons JHH = +0.63 Hz. Hence an
A2M3X is observed where the OOCH proton is set voluntarily to X. (Correct would be a
nomenclature like AM2X3). Signs of coupling constants were established by double resonance. K.
Hayamizu, O. Yamamoto; J. Mol. Spec. 23, 121-130 (1967).
Ethanol CH3CH2OH
1
The 500 MHz H NMR spectrum of dry Ethanol in CDCl3 exhibits an A2BX3 close to A2MX3 system.
If a trace of HCl is added to ethanol in CDCl3 than a neat A2X3 is observed. By rapid proton transfer
reaction the OH proton is decoupled.
3.72 3.70 3.68 3.66 3.64 3.62 3.60 3.58 3.56 3.54 3.52 3.50 3.48
(ppm )
CH2 OH
1
Figure 449 : Experimental 500 MHz H NMR spectrum of dry Ethanol in CDCl3. A2B part of A2BX3.
NMR Data for Ethanol
Parameter Ethanol Dry Ethanol + HCl

A2BX3 A2X3
δH(CH2) 3.6719 3.7610
δH(OH) 3.5147 -
δH(CH3) 1.2146 1.2243

3
JHCOH 4.89 -
3
JHCCH 7.02 7.03
4
JHCCOH n. r. -
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Ethylfluoride - CH3CH2F
Ethylfluoride may be described by an A2B3X spin system. But second order is visible only at low
fields (≤ 60 MHz). At higher fields neat A2M3X spectra are detected and first order analysis is
straightforward.
NMR Data for Ethylfluoride
Parameter Type Data

δ1 δH(A2) 4.36 ppm
δ2 δH(M3) 1.24 ppm
δ3 δF(X) 214 ppm

3
J12 JAM = JHH 6.90 Hz
2
J13 JAX = JFH 46.70 Hz
3
J23 JMX = JFH 25.20 Hz
910 900 890 880 870 860 850 840

(Hz)
280 270 260 250 240 230 220 210

(Hz)
Figure 450 : Simulated 200 MHz H NMR spectrum. Upper: CH3CH2F. νH(A2) = 872 Hz. HWB = 0.3 Hz.
1
Lower: CH3CH2F. νH(M3) = 248 Hz. HWB = 0.3 Hz.
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621
40360 40320 40280 40240 40200 40160

(Hz)
F NMR spectrum. CH3CH2F. νF(X) = 40264.89 Hz.

19
Figure 451 : Simulated 188.154 MHz
Data from: S. L. Stafford, J. D. Baldeschwieler; J. Amer. Chem. Soc. 83, 473-4474 (1961).
11.3 Organophosphorus Compounds CH3CH2P(O)Cl2 /

CH3CH2OP(O)Cl2
1
At high fields those compounds give rise to A2M3X H NMR spectra. Corresponding NMR data are
listed below:
NMR Data for CH3CH2P(O)Cl2 / CH3CH2OP(O)Cl2
Parameter CH3CH2P(O)Cl2 CH3CH2OP(O)Cl2

δ1 A2 2.6244 4.4099 ppm
δ2 M3 1.4123 1.4999 ppm
δ3 X 52,5 0.0 ppm

3 3
J12 JAM 7.40 JHH 7.0860 JHH Hz
2 3
J13 JAX -14.80 JPH 11.2860 JPH Hz
3 4
J13 JMX 30.20 JPH 1.2420 JPH Hz
HWB global 0.3 0.3 Hz
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1340 1330 1320 1310 1300 1290

(Hz)
730 720 710 700 690 680

(Hz)
1
Figure 452 : 500 MHz H NMR spectrum. Upper: CH3CH2P(O)Cl2. CH2 region. Lower: CH3CH2P(O)Cl2.
CH3 region.
Inspect the surprisingly primitive A2 part from the A2M3X spectrum of CH3CH2P(O)Cl2.: a “sextet”
with intensities 1:3:4:4:3:1. This “sextet” structure will appear if JAM :JAX = 1:2 .
3 2
And this is true for CH3CH2P(O)Cl2 : JAM = JHH = 7.4 Hz and JAX = JPH = -14.8 Hz.
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1
Now compare the H NMR spectrum of CH3CH2O-P(O)Cl2:
2220 2210 2200 2190

(Hz)
760 755 750 745 740

(Hz)
1
Figure 453 : Simulated 500 MHz H NMR. Upper: CH3CH2OP(O)Cl2. CH2 region. Lower:
CH3CH2OP(O)Cl2. CH3-region.
Exercise: For didactical purposes study low field spectra of higher complexity. Simulate and re-
1
analyze the 90 MHz H NMR spectrum of CH3CH2P(O)Cl2 using data given above.
1
The original experimental 90 MHz H NMR spectrum of CH3CH2P(O)Cl2 was analyzed by M.
Engelhardt, PhD Thesis 1986, Heinrich-Heine-University Düsseldorf).
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11.4 Non-equivalence Effects in ABC3X 1H NMR and [ABC3]2X

31
P NMR Spectra
1 31
Non-equivalence effects in ABC3X in H NMR and [ABC3]2X in P NMR spectra from diethyl-
substituted phosphorous compounds (CH3CH2)2P(E)E´H (E, E´= O, S) were studied in
(CH3CH2)2P(O)OH, (CH3CH2)2P(O)SH, (CH3CH2)2P(S)OH and (CH3CH2)2P(S)SH.
Diethyldithiophosphinic acid (CH3CH2)2P(S)SH in benzene exist dominantly as a monomer with

minor contribution from a dimer:
R S H S R
P P
R S H S R
In contrast hereto diethylphosphinic acid (CH3CH2)2P(O)OH in benzene forms dominantly the

corresponding dimer with some contribution from a trimer:
R R
O O
H H
O O
R P O H O P R
R R
The situation is more complex for diethylmonothiophosphinic acid which at lower concentrations
exists in two tautomeric forms (CH3CH2)2P(S)OH and (CH3CH2)2P(O)SH with the tendency - at
higher concentrations - to form additional dimers as well:
R S H O R R O H S R
P P P P
R O H S R R S H O R
1
H NMR spectra of (CH3CH2)2P(O)OH, (CH3CH2)2P(S)OH, and (CH3CH2)2P(S)SH may be handled
31
as ABC3X pattern while P NMR spectra correspond to [ABC3]2X. No evidence for long range
n
couplings JHH (n = 4-6, across phosphorus) was found from experimental spectra. [Bear in mind:
n
long range couplings JFF (n = 4-6, across phosphorus) exist in [ABM3]2X systems from
(CF3CF2)2P-derivatives].
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As an example data for diethyldithiophosphinic acid (CH3CH2)2P(S)SH are shown below:
1
H NMR Data of (CH3CH2)2P(S)SH. 25% in CDCl3. TMS int. ref..
Parameter Parameter Type Data

δi [ppm]
1 A H 2.1890
2 B H 2.1831
3 M3 H 1.3271
4 X P 76.5
Jik [Hz]
2
12 AB JHH -12.000
3
13 AM JHH 7.163
2
14 AX JPH -10.578
3
23 BM JHH 7.867
2
24 BX JPH -10.265
3
34 MX JPH 22.163
HWBi [Hz]
1 A H 0.5
2 B H 0.5
3 M3 H 0.4
Data: W. Kuchen, M. Fuchs, G. Hägele; unpublished.
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1 31
Exercise: Calculate H and P NMR spectra as indicated below.
220 200 180 160 140 120 100

(Hz)
1
Figure 454 : Example 1: 90 MHz H NMR spectrum. (CH3CH2)2P(S)SH, 25% in CDCl3.
-920 -960 -1000 -1040 -1080

(Hz)
31
Figure 455 : Example 2: 36.4 MHz P NMR spectrum (CH3CH2)2P(S)SH, 25% in CDCl3.
Exercise: Calculate 500 MHz / 202.4 MHz spectra and do sub-spectral analysis.
Exercise: Neglect non-equivalence effects in ethyl groups: approximate the ABC3X case by an
averaged D2E3X case. Set: δD = (δA+δB)/2. δE = δC. JDE = (JAC+JBC)/2. JDX = (JAX+JBX)/2. Compare
spectral patterns.
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11.5 Non-equivalence Effects in Geminal Pairs of Enantiotopic

Ethoxy Groups
Non-equivalence effects in geminal pairs of enantiotopic ethoxy groups generate ABC3X to ABM3X
spectra in RP(OCH2CH3)2, RP(O)(OCH2CH3)2, and RP(S)(OCH2CH3)2.
H H R H H
C P C
H 3C O O CH3
H H O R H H H H S R H H
C P C C P C
H 3C O O CH3 H 3C O O CH3
11.5.1 Example 1: C6H5P(OCH2CH3)2
H H
O CH2 CH3
H P
O CH2 CH3
H H
NMR data from a meticulous 60 MHz A2B3X analysis of diethylphenylphosphonite (10% in CCl4)
were described by M. P. Williamson, C. E. Griffin; J. Phys. Chem. 72, 4043-4047 (1968).
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Under those conditions methylene protons appeared to be equivalent forming the A2 composite
particle.
NMR Data for C6H5P(OCH2CH3)2 (10% in CCl4)
δi Data
δ1 3.9538 A2 H
δ2 1.2616. M3 H
3
J12 7.0670 JAM JHH
3
J13 7.7350 JAX JPH
4
J23 0.4940 JMX JPH
1
Starting off from those data a hypothetical 200 MHz H NMR spectrum was simulated, which
intrigued us to re-measurements of C6H5P(OCH2CH3)2 at 200 MHz. The methyl part appears as a
simple triplet of doublets but the methylene pattern is more complex.
Obviously the methylene protons are non-equivalent under those experimental conditions and an
ABM3X system is monitored.
1 31
The phosphorous decoupled H{ P} spectrum from ethoxy groups in C6H5P(OC2H5)2 - an
ABM3 System.
H H
O CH2 CH3 H H A
H P O C C H M3
O CH2 CH3 H H B
H H
The total proton spectrum shows two separate regions, each generated by typical 5-spin systems:
The aromatic protons give rise to an [AB]2C spectrum, which will not be discussed here. b) Both
ethoxy groups in the P(OC2H5)2 unit are equivalent.
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1 31
Hence in H{ P} it suffices to analyze the CH2CH3 skeleton, exhibiting the characteristic ABM3
pattern at 200 MHz or higher frequencies. NMR parameters were obtained by iterative analysis of
1 31
the 200 MHz H{ P} spectrum as shown below:
1 31
200 MHz H{ P} NMR Parameters of C6H5P(OC2H5)2, 5% in CDCl3, int. ref. TMS.
δA δH 3.7935 ppm
δB δH 3.6835 ppm
δM δH 1.0789 ppm
νA νH 758.691 Hz
νB νH 736.699 Hz
νM νH 215.773 Hz
2
JAB JHH -10.275 Hz
3
JAM JHH 7.090 Hz
3
JBM JHH 7.090 Hz
1 31
The ethoxy part of a 200 MHz H{ P} NMR spectrum from C6H5P(OC2H5)2 (5% in CDCl3, int. ref.
TMS) shows the expected triplet for two isochronous methyl groups responsible for the M3 part of
this ABM3 system. The AB part is slightly more complex.
780 775 770 765 760 755 750 745 740 735 730 725 720 715 710
( Hz)
1 31
Figure 456 : Ethoxi groups. AB part of phosphorous decoupled 200 MHz H{ P} NMR spectrum from
C6H5P(OC2H5)2, 5% in CDCl3, int. ref. TMS. Simulated with DAISY.
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The AB part of this ABM3 system effectively breaks down into four ab sub-spectra:
1 31
Figure 457 : Simulated AB part of 200 MHz H{ P} NMR spectrum from C6H5P(OC2H5)2, 5% in CDCl3.
Traces 1 to 5 from top to bottom in graphic. Trace 1: total AB part of ABM3 spectrum, traces 2 to 5
corresponding ab sub-spectra. Trace 2: mM3 = +3/2. Trace 3: mM3 = +1/2. Trace 4: mM3 = -1/2.
Trace 5: mM3 = -3/2.
The four ab sub-spectra are determined by effective Larmor frequencies νa and νb , and the
2
characteristic coupling constant JAB = JHH. Effective Larmor frequencies are functions of Larmor
frequencies νA, νB, and coupling constants JAM = JHH, JBM = JHH resp.:
3 3
νa =ν A + mM ⋅ JAM
3
νb =νB + mM ⋅ JBM
3
Each sub-spectrum is affiliated with a statistical weight w:
()
w = nk where n = 3 and k=
n
2
− mM
3
In principle standard ABM3 analysis from 1D HR NMR spectra does not yield the signs of coupling
2 3 3
constants, only the magnitudes of coupling constants JAB = JHH, JAM = JHH, JBM = JHH are
2
obtained. From a multitude of investigations it is well established that: sign( JHH) = negative and
3
sign( JHH ) = positive. In C6H5P(OC2H5)2 the vicinal proton-proton coupling constants follow
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JAM ≅ JBM . Hence the analysis of the phosphorous decoupled proton NMR spectrum is straight
forward.
1
The phosphorous coupled H spectrum from Ethoxy groups in C6H5P(OC2H5)2 - an
ABM3X System
H H
O CH2 CH3 H H A
H P P O C C H X M3
O CH2 CH3 H H B
H H
1
NMR parameters were obtained by iterative analysis of the 200 MHz H spectrum as shown below
in a table:
1
200 MHz H NMR Parameters of C6H5P(OC2H5)2, 5% in CDCl3, int. ref. = TMS.
δA δH 3.7935 ppm
δB δH 3.6835 ppm
δM δH 1.0789 ppm
δX δP ppm
νA νH 758.691 Hz
νB νH 736.699 Hz
νM νH 215.773 Hz
νX νP -1000.000 Hz
2
JAB JHH -10.275 Hz
3
JAM JHH 7.090 Hz
3
JAX JPH 8.826 Hz
3
JBM JHH 7.090 Hz
3
JBX JPH 14.498 Hz
4
JMX JPH 0.593 Hz
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The M3 part of this ABM3X system appears as doublet of triplets for two isochronous methyl
groups. The AB part is more complex and can be broken down in 8 ab sub-spectra:
780 775 770 765 760 755 750 745 740 735 730 725 720 715 710
( Hz)
1
Figure 458 : AB part of 200 MHz H NMR spectrum from C6H5P(OC2H5)2, 5% in CDCl3, int. ref. TMS.
8 ab Sub-spectra
1
Figure 459 : AB part of 200 MHz H NMR spectrum from C6H5P(OC2H5)2. Upper trace: total AB part of
ABM3X spectrum, other traces; corresponding ab sub-spectra, Red: mX = -½. blue: mX = +½.
31 1 31
For sub-spectral breakdown according to mM see P-decoupled H{ P} NMR spectrum above.
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The eight ab sub-spectra are determined by effective Larmor frequencies νa and νb , and the
2
characteristic coupling constant JAB = JHH. Effective Larmor frequencies are functions of Larmor
frequencies νA, νB, and coupling constants JAM = JHH, JBM = JHH, JAX = JPH, JBX = JPH, resp..
3 3 3 3
νa =ν A + mM ⋅ JAM + mX ⋅ JAX
3
νb =νB + mM ⋅ JBM + mX ⋅ JBX

3
Each sub-spectrum is affiliated with a statistical weight w:
w = nk() where , k=
3
2
− mM and mM =
3 3
3 1 1 3
(− , − , + , + )
2 2 2 2
2 3 3 3 3
ABM3X analysis does not yield signs for JAB = JHH, JAM = JHH, JBM = JHH, JAX = JPH, JBX = JPH. But
2 3 3
it is well established that: sign( JHH) = (-), sign( JHH ) = (+), and sign( JPH ) = (+). In C6H5P(OC2H5)2
the vicinal phosphorus-proton couplings constants follow JAX ≠ JBX . JPH depends on the dihedral
3
angles involved in the skeleton of P-O-C-H. Hence the ABM3X analysis is slightly more complex.
1
Spectra and Data: The 200 MHz H NMR study of C6H5P(OC2H5)2 presented above was
performed by R. Boetzel, Düsseldorf.
Remark: Chemical shift δP(C6H5P(OCH2CH3)2) = 154 ppm. V. Mark, C. H. Duncan, M. Crutchfield,

31 31
J. R. van Wazer; “Compilation of P NMR Data”, chapter 4, 227-457, in “P Nuclear Magnetic
Resonance”, edits. M. M. Crutchfield, C. H. Duncan, J. H. Letcher, V. Mark, J. R. van Wazer,
“Topics in Phosphorus Chemistry”, Volume 5, J. Wiley & Sons, 1967. An old but still useful
collection of δP data.
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11.5.2 Example 2: C6Cl5P(OCH2CH3)2
Solvent activated phosphonylation of hexachlorobenzene with sodium diethylphosphite

unexpectedly lead to pentachlorophenylphosphonous acid diethylester C6Cl5P(OC2H5)2 which was
characterized by 200 MHz NMR studies. An ABM3X spectrum was observed where the AB part is
shown below:
890 880 870 860 850 840

(Hz)
Figure 460 : 200 MHz NMR spectrum from C6Cl5P(OC2H5)2 - methylene protons
Corresponding data from iteration of C6Cl5P(OC2H5)2 with DAISY are listed in the following table.
For comparison data are given for related structures C6Cl5P(O)(OC2H5)2 and C6Cl5P(S)(OC2H5)2.
Data from:
a) W. Boenigk; PhD Thesis 1984, Heinrich-Heine-Universität Düsseldorf.
b) W. Boenigk, G. Hägele; Chem. Ber. 117, 2287-2292 (1984).
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1
200 MHz H NMR Data from C6Cl5P(OC2H5)2, C6Cl5P(O)(OC2H5)2 and C6Cl5P(S)(OC2H5)2
Parameter C6Cl5P(OC2H5)2 C6Cl5P(O)(OC2H5)2 C6Cl5P(S)(OC2H5)2

δ1 A 4.3175 4.2942 4.3345 ppm
δ2 B 4.2970 4.2169 4.2587 ppm
δ3 M3 1.3149 1.3887 1.4087 ppm
δ4 X 164.7 8.7 72.1 ppm
ν1 A 863.50 858.83 866.90 Hz
ν2 B 859.94 843.37 851.73 Hz
ν3 M3 262.98 277.75 281.75 Hz
ν4 X 13334.23 704.36 5837.27 Hz

2
J12 JHH -10.41 -10.07 -10.11 Hz
3
J13 JHH 7.39 7.11 7.08 Hz
3
J14 JPH 10.22 8.08 9.12 Hz
3
J23 JHH 6.65 7.03 7.01 Hz
3
J24 JPH 9.11 8.72 11.87 Hz
4
J34 JPH n.r. 0.66 n.r. Hz
HWB 0.3 0.3 0.3 Hz
Note: The difference in chemicals shifts ∆δAB from C6Cl5P(OC2H5)2 is smaller than ∆δAB from
C6H5P(OC2H5)2. It seems justified to assume, that the aromatic ring current effect in
C6Cl5P(OC2H5)2 is smaller than in C6H5P(OC2H5)2.
1
Exercise: Simulate and reanalyze H NMR spectra of C6Cl5P(O)(OC2H5)2 and C6Cl5P(S)(OC2H5)2.
Ethoxy Groups Attached to Prochiral and Chiral Phosphorous Centers
H R H H R1
H 3C C O P O C CH3 H 3C C O P R2
H O H H Z
M3 A,B X A,B M3 M3 A,B X
Type 1 Type 2
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Type 1: Methylene protons are enantiotopic, in proximity to pro-chiral phosphorous, and

magnetically non-equivalent. An ABC3X to ABM3X is formed.
Type 2: Methylene protons are diastereotopic, in proximity to chiral phosphorous, and magnetically
non-equivalent. Spectra appear as ABC3X to ABM3X types.
The following examples compare ethylesters from phosphonic and phosphinic acids resp.
1 2 1 2
R R P(O)OCH2CH3 where R = CCl2=CH-CH2- and R = CH3CH2O-, CH3-, C6H5.
NMR Data for Ethoxy Compounds with Pro-chiral and Chiral Phosphorous Centers
CCl2=CH-CH2- CCl2=CH-CH2- CCl2=CH-CH2-

Par. Type Type
P(O)(OC2H5)2 P(O)(CH3)OC2H5 P(O)(C6H5)OC2H5
P-pro-chiral P-chiral P-chiral + P-Ph
δ1 A 3.8583 4.1145 4.1387
δ2 B 3.8376 4.0913 3.9562
δ3 M3 1.0139 1.3475 1.3316
δ4 X 23.809 49.601 38.395
ν1 A 771.66 822.89 827.74
ν2 B 767.52 818.26 791.23
ν3 M3 202.78 269.50 266.31
ν4 X 1927.6 4015.7. 3185.5
ν1-ν2 νA-νB 4.14 4.63 36.51

2
J12 AB JHH -10.18 -10.02 -10.09
3
J13 AM JHH 7.28 7.11 7.04
3
J14 AX JPH 8.88 7.81 7.64
3
J23 BM JHH 6.91 6.93 7.04
3
J24 BX JPH 8.69 8.28 7.79
4
J34 MX JPH n. r. n. r. n. r.
HWB 0.3 0.3 0.3
Note: Increase of ∆δ = δH(A)-δH(B) in R R P(O)OCH2CH3 by aromatic substituent C6H5.

1 2
Data from: U. Prior, PhD Thesis 1992, Heinrich-Heine-University Düsseldorf.
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1 2
Simulated spectra for methylene regions from R R P(O)OCH2CH3 are shown below:
800 780 760 740

(Hz)
Figure 461 : Simulated 200 MHz NMR spectrum of CCl2=CH-CH2-P(O)(OCH2CH3)2
860 840 820 800 780

(Hz)
Figure 462 : Simulated 200 MHz NMR spectrum of CCl2=CH-CH2-P(O)(CH3)OCH2CH3
840 820 800 780

(Hz)
Figure 463 : Simulated 200 MHz NMR spectrum of CCl2=CH-CH2-P(O)(C6H5)OCH2CH3
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11.6 Aromatic Substituents Attached to C-Chiral Centers
Aromatic substituents attached to C-chiral centers increase the non-equivalence effects in 1H NMR
spectra of ethoxy groups. Isatine reacts with diethylphosphite to yield 3-diethoxyphosphoryl-3-
hydroxyindolin-2-on, alternatively named 3-hydroxy-2-oxoindolin-3-ylphosphonic acid diethylester.
H O H
HO P(O)(OCH2CH3)2
H O H O
HP(O)(OCH2CH3)2
N N
H H H H
H H
This C-chiral compounds exhibits enantiotopic ethoxy groups and each pair of methylene protons is
enantiotopic as well. Hence we expect the overlap of ABM3X and EFR3X spectra together with an
ABCDX system of the aromatic protons.
1
Figure 464 : Total 200 MHz H NMR spectrum simulated for 3-hydroxy-2-oxoindolin-3-yl-phosphonic acid
diethylester in CD3OD.
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1
Figure 465 : Simulated 200 MHz H NMR spectrum of 3-hydroxy-2-oxoindolin-3-yl-phosphonic acid
diethylester in CD3OD. Aliphatic region. HWB = 0.3 Hz.
1
200 MHz H NMR Parameter [Hz]
ABM3X EFR3X
Parameter Parameter Left POC2H5 Right POC2H5
νA νH 854.062 816.161
νB νH 849.783 799.350
νM νH 269.596 234.810
3
JAM JHH 7.035 7.061
3
JAX JPH 8.448 7.416
3
JBM JHH 7.129 7.072
3
JBX JPH 7.623 8.506
4
JMX JPH 0.606 0.639
HWB 0.3 0.3
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For Completeness - Here the Aromatic Region
HA
HO P(O)(OEt)2
HC O
N
HB H
HD
7.50 7.35 7.20 7.05 6.90

(ppm)
1
Figure 466 : Simulated 200 MHz H NMR spectrum of 3-hydroxy-2-oxoindolin-3-yl-phosphonic acid
diethylester in CD3OD. Aromatic region. HWB = 0.3 Hz.
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1
200 MHz H NMR Parameter [Hz]
Parameter Parameter ABCDX

νA νH 1502.000
νB νH 1461.700
νC νH 1413.040
νD νH 1380.120
4
JAB JHH 1.338
3
JAC JHH 7.599
5
JAD JHH 0.632
4
JAX JPH 2.106
3
JBC JHH 7.665
3
JBD JHH 7.840
6
JBX JHH 1.741
4
JCD JHH 1.020
5
JCX JHH 0.506
5
JDX JHH 1.162
Remark: Synthesis and NMR from R. Peters and G. Hägele, Düsseldorf. Thanks are due to J.
Voss, Hamburg, for help with nomenclature.
Another, more advanced, example where TopSpin / DAISY successfully handles a 22 spin
1
problem follows below for the 200 MHz H NMR spectrum of 1-N-(4´-fluorophenyl)-amino-1-
phenylmethanephosphonic acid diethylester.
1
Figure 467 : Experimental 200 MHz H NMR spectrum of p-C6H4F-NH-CH(C6H5)-P(O)(OCH2CH3)2 (2% in
CDCl3, int. ref. TMS, at ambient temperature).
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The total spectrum is divided into five regions:

Regions 1 and 2 are affiliated with two [AB]2C and [AB]2 systems from the aromatic substituents
C6H5 and C6H4F.
Region 3 is characteristic for the AX doublet due to the HNCHP proton while the HNCP proton
seems to be “invisible” on first sight.
Regions 4 and 5 reveal an overlap of two ABM3X and EFR3X systems from the pair of non-
equivalent ethoxy groups. Ethoxy groups and methylene protons are enantiotopic.
Region Range [ppm] Assignments

1 7.20 - 7.50 C6H5 aromatic protons from ring 2
2 6.45 - 6.90 p-C6H4F aromatic protons from ring 1
3 4.60 - 4.80 C-HN-CHP-C methane fragment with chiral C atom
4 3.55 - 4.30 2 Methylene groups (POCH2CH3)
5 1.05 - 1.35 2 Methyl groups (POCH2CH3)
An additional weak singlet is detected at 7.2617 ppm which is due to CHCl3 from commercial
CDCl3 solvent. The ABM3X is closer than EFR3X to the phenyl ring C6H5, while EFR3X is much
closer than ABM3X to the p-fluorophenyl ring p-C6H4F. Compare the molecular structure below. We
assume that the upfield shift due to aromatic ring current effects is stronger in ABM3 than in EFR3X.
Initial iterations on the total spectrum with TopSpin / DAISY using 22 spins (NH proton excluded)
n
showed that benzylic couplings JHH (n = 4-6) are negligibly small, hence the model of five
n
fragments is justified. But benzylic type couplings JPH (n = 4-6) were found.
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Region 1 - [AB]2CX from C6H5-CHNP
1
200 MHz H NMR Parameters [Hz] for [AB]2CX from Ring 1 C6H5-CHNP
Parameter Parameter Parameter Best Standard

ν1 = ν 2 νA = νA´ 1490.56290 0.00477
ν3 = ν 4 νB = νB´ 1466.66778 0.00584
ν5 νC 1454.18369 0.00959
4
J12 JHH JAA´ 2.04677 0.01716
3
J13 = J24 JHH JAB 7.80517 0.00863
5
J14 = J23 JHH JAB´ 0.54833 0.00892
4
J15 = J25 JHH JAC 1.17829 0.00893
J16 = J26 JPH JAX 2.41670 0.00886
4
J34 JHH JBB´ 1.29356 0.01904
3
J35 = J45 JHH JBC 7.43643 0.01207
5
J36 = J46 JPH JBX -0.86136 0.01182
6
J56 JPH JCX 2.11103 0.01857
HWB 0.76176 0.00603
BO -0.17609 0.01349
BA -0.00218 0.00028
First frequency point = 1505.21923 Hz. Last frequency point = 1437.53874 Hz.
Number of points = 1305. Digital resolution = 0.05190 Hz/Point.
Standard Deviation of Measurements = 0.195205. R-Factor = 0.613665 ( % ).
BO = Base line offset. BA = Base line ascent.
7.55 7.50 7.45 7.40 7.35 7.30 7.25 7.20 7.15

(ppm)
1
Figure 468 : 200 MHz H NMR spectrum of p-C6H4F-NH-CH(C6H5)-P(O)(OCH2CH3)2 (2% in CDCl3, int.
ref. TMS, amb. temp.). Upper: experimental. Lower: Iterated.
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Region 2 - [AB]2X from C6H4F
1
200 MHz H NMR Parameters [Hz] for [AB]2X from Ring 2 C6H4F-NHC
Parameter Parameter Best Standard

ν1 = ν 2 νH 1305.03995 0.00233
ν3 = ν 4 νH 1359.66824 0.00241
4
J12 JHH 2.96159 0.01727
3
J13 = J24 JHH 8.86825 0.00472
5
J14 = J23 JHH 0.33782 0.00585
4
J15 = J25 JFH 4.40264 0.00460
4
J34 JHH 3.07910 0.01730
3
J35 = J45 JFH 8.45304 0.00451
HWB 0.66655 0.00413
Standard Deviation of Measurements = 0.192265. R-Factor = 1.193186 %.
6.85 6.80 6.75 6.70 6.65 6.60 6.55 6.50 6.45

(ppm)
1
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Region 3 - HNCHP
A doublet is found for the CHP group. Apparent broadening might be due to neighboring nitrogen
14
N spin. No evidence for benzylic couplings C6H5-CHPN was found (by HH-COSY and iteration).
1
200 MHz H NMR Parameters [Hz] for HNCHP
Parameter Best Standard

νH 938.51056 0.00042
2
JPH -24.15565 0.00085
HWB 1.70962 0.00120
BO 0.26173 0.01172
BA 0.00679 0.00030
4.90 4.85 4.80 4.75 4.70 4.65 4.60 4.55 4.50

(ppm)
1
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Regions 4 and 5 - 2 Ethoxy Groups in P(O)(OCH2CH3)2
ABM3X and EFR3X systems characterize the pair of non-equivalent ethoxy groups:
1
200 MHz H NMR Parameters [Hz] for P(O)(OCH2CH3)2
ABM3X Ethoxy Group 1 EFR3X Ethoxy Group 2

Parameter Parameter Best Standard Best Standard
ν1 ν1 785.45870 0.00356 827.01367 0.00581
ν2 ν2 733.60116 0.00420 819.75192 0.00557
ν3 ν3 220.90975 0.00095 257.16395 0.00096

2
J12 JHH -10.12416 0.00564 -10.15709 0.02253
3
J13 JHH 7.05016 0.00405 7.02906 0.00572
3
J14 JPH 7.29560 0.00941 7.56360 0.00810
3
J23 JHH 7.07600 0.00407 7.10519 0.00570
3
J24 JPH 8.31534 0.00765 8.38352 0.00841
4
J34 JPH 0.65343 0.00174 0.54688 0.00157
HWB 0.58617 0.00187 0.59110 0.00191
Region 4:
Number of points = 3677.
Region 5:
Number of points = 1894.
Region 4 and 5:
Digital resolution = 0.05190 Hz/Point. Total Number of spectral points = 5571.
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Region 4: Methylene Protons
1
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Region 5: Methyl Protons
1.50 1.40 1.30 1.20 1.10 1.00 0.90

(ppm)
R3 M3
1
The assignment of AB to M3 and EF to R3 for ethoxy groups was confirmed by HH-COSY at

600 MHz (not shown here).
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Addendum to region 3: So far so good, but where is the signal from the NH proton in
HNCHP? It is hidden in region 3, close to the HNCHP signal. A tentative iteration for HNCHP as a
singlet yields a very broad signal: δH = 4.95 ppm. νH = 990.66 Hz. HWBeff = 240 +/- 37 Hz. Results
from solvent and VT temperature studies on p-C6H4F-NH-CH(C6H5)-P(O)(OCH2CH3)2 leads to
more details: HN-CHP gives rise to an ABX system in HAN-CHBPX:
1
Figure 473 : 200 MHz H NMR spectrum of p-C6H4F-NH-CH(C6H5)-P(O)(OCH2CH3)2 4% in CDCl3 at -
40°C.
1
Figure 474 : 200 MHz H NMR spectrum of p-C6H4F-NH-CH(C6H5)-P(O)(OCH2CH3)2 4% in C6D5CD3 at
+60°C.
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VT NMR Data for the NH-CHP Skeleton from p-C6H4F-NH-CH(C6H5)-P(O)(OCH2CH3)2
4% in CDCl3 1% in C6D5CD3
Parameter Type
at -40°C at +60°C
δA 4.9592 5.018 ppm
δB 4.7733 4.635 ppm
νA 991.849 1003.6 Hz
νB 954.669 926.9 Hz
3
JAB JHH 7.938 5.8 Hz
3
JAX JPH 9.827 9.5 Hz
2
JBX JPH -24.717 -24.1 Hz
HWBA HWBA 3.329 10 Hz
HWBB HWBB 2.678 5.5 Hz
14
In fact, the HN-CHP skeleton is even more complex since quadrupolar nitrogen N (I = 1) is
involved in a total ABMX system from HANM-CHBPX giving rise to relaxation and line broadening
3
effects. Note: At room temperature JHH is not resolved for HN-CHP and a simple doublet results.
References
a) Iterations of total spectrum: R. Spiske; PhD Thesis 1996, Heinrich-Heine-University

Düsseldorf.
b) b) Synthesis and NMR spectra: U. Gruss; PhD Thesis 1997, Heinrich-Heine-University
Düsseldorf.
c) c) Selective iterations and review: G. Hägele; “Physical Properties and NMR-Spectroscopic
Characterisation of Aminophosphonates and Amino-phosphinates”, p. 217-284, in
“Aminophosphonic and Aminophosphinic Acids”, Edits. V. P. Kukhar, H. R. Hudson; John
Wiley & Sons, Chichester, 2000.
For aromatic ring current effects read:

a) C. E. Johnson, F. A. Bovey; J. Chem. Phys. 29, 1012-1014 (1958).
b) C. W. Haigh, R. B. Mallion; Org. Magn. Res. 4, 203-228 (1972).
c) R. J. Abraham; Org. Magn. Res. 9, 367-373 (1977). d) R. J. Abraham; NMR in Mol. Biol.
461 (1978).
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11.7 An ABM3X Spin System from 1-Chloro-2-fluoro-2-bromo-

propane
Compare the spectral pattern from 1-chloro-2-fluoro-2-bromo-propane CH2Cl-CFBr-CH3 with

ABM3X type spectra from CH3-CH2-O-P shown above.
CCl4 Acetone
δA δH 4.1417 4.2584 [ppm]
δB δH 3.8996 4.1761 [ppm]
δM δH 2.1857 2.2042 [ppm]
δX δF
a
17.93 - [ppm]
2
JAB JHH -12.226 -12.380 [Hz]
4
JAM JHH 0.747 0.683 [Hz]
3
JAX JFH 8.193 11.037 [Hz]
4
JBM JHH 0.223 0.196 [Hz]
3
JBX JFH 25.635 23.609 [Hz]
3
JMX JFH 18.990 19.564 [Hz]
Data from: R. J. Abraham, W. L. Oliver, Jr.; Org. Magn. Res. 3, 725-732 (1971).
a)
δF is referenced vs. CF3CCl3 where δF(CFCl3) = -100.25 ppm.
This paper presents excellent spectra, precise results and a discussion of intramolecular rotation
and solvent effects. A good example for sub-spectral analysis.
Exercise: Simulate spectra.
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Seven and More Spins: C3 to C5 Alkyl Groups
12 Seven and More Spins:

C3 to C5 Alkyl Groups
Some spectra and comments regarding propyl-, butyl- and pentyl-compounds
12.1 CH3-CH2-CH2-R - n-Propyl Compounds
1
Schrumpf studied the H NMR spectra of two different series of n-propyl compounds which lead to
A2B2C3 and [AB]2C3 spin systems. Sub-spectral analytical methods were described in details.
Series A Series B
R = Cl, Br, I R = CHO, COCH3

O-nC3H7 COOC2H5, CN
JAC
JAC JAB
H H JBC B A
C3 B2 A2 CH3 C C R C3 JBB´ JAB´ JAA´
H H B´ A´
JBC JAC
A2B2C3 [AB]2C3
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1
Series A, the n-propyl halides and the di-n-propyl ether, give rises to deceptive simple A2B2C3 H
NMR spectra:
NMR Parameters of CH3-CH2-CH2-X
X
Parameter O-CH2-CH2-CH3 Cl Br I
νA -395.63 -384.76 -397.27 -415.85
νB -570.08 -553.74 -546.67 -549.08
νC -633.78 -629.49 -630.20 -633.03

JAB 6.45 6.60 6.67 6.80
JAC 0.0 -0.06 -0.05 -0.05
JBC 7.43 7.35 7.29 7.25
All values are given in Hz, resonance frequencies are measured at 100 MHz relative to internal
benzene C6H6. Accuracy of resonance frequencies: ± 0.05 Hz, of coupling constants: ± 0.03 Hz.
CH3CH2CH2Cl
-3.6 -4.0 -4.4 -4.8 -5.2 -5.6 -6.0 -6.4

(ppm)
1
Figure 475 : Simulated 100 MHz H NMR spectrum of CH3CH2CH2Cl. A2B2C3 system. Ca. 90% in C6H6.
Note original data: δH(C6H6) = 0 Hz!
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At high fields A2B2C3 approximate the deceptively simple A2M2X3 system as shown below:
-3.6 -4.0 -4.4 -4.8 -5.2 -5.6 -6.0 -6.4

(ppm)
1
Figure 476 : Hypothetical 500 MHz H NMR spectrum of CH3CH2CH2Cl. Approximates A2M2X3 system.
Ca. 90% in C6H6. Note original data: δH(C6H6) = 0 Hz!
1
Series B gives rise to more complex [AB]2C3 H NMR spectra:
NMR Parameters of CH3-CH2-CH2-X
X
a) b)
Parameter CHO COCH3 COOC2H5 CN
νA -497.01 -494.80 -508.20 -507.69
νB -570.40 -578.06 -569.04 -575.17
νC -639.10 -641.15 -637.55 -633.98

JAB+JAB´ 14.41 14.50 14.68 14.07
JAB-JAB´ 0.96 1.66 0.92 -
JAC -0.10 -0.10 -0.12 -0.05
JBC 7.45 7.41 7.43 7.39
JAA´-JBB´ -3.0 -3.25 -2.01 -
All values are given in Hz, resonance frequencies are measured at 100 MHz relative to internal
benzene. Accuracy of resonance frequencies is 0.05 Hz, that of the coupling constants 0.03 Hz.
Data obtained by H{ H} decoupling the CHO proton. Additional data from H NMR: νH(CHO) =
a) 1 1 1
3 4
237.2 ±0.1 Hz. JHH(CH2CHO) = 1.70 ±0.03 Hz. JHH(CH2CH2CHO) = 0.06 ± 0.03 Hz.
b)
νH(COCH3) = -528.4 ± 0.1 Hz. 4JHH(CH2COCH3) = 0.46 ± 0.05 Hz.
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12.1.1 Example: CH3-CH2-CH2-CHO
The aldehyde proton couples to the α-methylene group with JHH = 1.7 Hz. Long range couplings to
3
β-methylene and γ-methyl groups are negligible ( JHH = 0.06 Hz and JHH = not resolved). A total
4 5
[AB]2C3X results (X = CHO).
2 1 0 -1 -2 -3 -4 -5 -6
(ppm)
1
Figure 477 : Total 100 MHz H NMR spectrum of CH3-CH2-CH2-CHO. Ca. 90% in C6H6. Note original
data: δH(C6H6) = 0 Hz!
2 1 0 -1 -2 -3 -4 -5 -6
(ppm)
1
Figure 478 : Hypothetical 500 MHz H NMR spectrum of CH3-CH2-CH2-CHO. Ca. 90% in C6H6. Note
original data: δH(C6H6) = 0 Hz!
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1190 1180
(Hz)
1
Figure 479 : Hypothetical 500 MHz H NMR spectrum of CH3-CH2-CH2-CHO.
-2460 -2470 -2480 -2490 -2500 -2510

(Hz)
1
Figure 480 : Hypothetical 500 MHz H NMR spectrum of CH3-CH2-CH2-CHO.
-2830 -2840 -2850 -2860 -2870

(Hz)
1
Figure 481 : 500 MHz H NMR spectrum of CH3-CH2-CH2-CHO
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-3170 -3180 -3190 -3200 -3210 -3220

(Hz)
1
Figure 482 : 500 MHz H NMR spectrum of CH3-CH2-CH2-CHO
Decoupling the aldehyde proton reduces the [AB]2C3X to an [AB]2C3 case.
-4.8 -5.2 -5.6 -6.0 -6.4

(ppm)
1 1
Figure 483 : Total 100 MHz H{ H} decoupled spectrum for CH3-CH2-CH2-CHO
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1 1
H{ H} decoupling at high fields approximates (but not fully reaches) the [AM]2X3 situation as shown
below:
-4.8 -5.2 -5.6 -6.0 -6.4

(ppm)
1 1
Figure 484 : 500 MHz H{ H} decoupled spectrum of CH3-CH2-CH2-CHO
-2460 -2470 -2480 -2490 -2500 -2510

(Hz)
1 1
Figure 485 : 500 MHz H{ H} decoupled spectrum for CH3-CH2-CH2-CHO
-2830 -2840 -2850 -2860 -2870

(Hz)
1 1
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-3170 -3180 -3190 -3200 -3210 -3220

(Hz)
1 1
12.1.2 Example: CH3-CH2-CH2-P(O)Cl2
1
90 MHz H NMR spectra of n-propyl phosphonic acid dichloride (30% in CDCl3) exhibit the high
second order habitus of an [AB]2C3X system.
JAC JAX
JBX
JAB
A B JBC
A B
JCX
JAA´ JAB´ JBB´ C3 X C3 X
A´ B´ A´ B´
1 31
Phosphorous decoupled H{ P} spectra reduced this problem to the slightly simpler [AB]2C3 case.
Increasing the field strength by using a 360 MHz spectrometer lead to [AB]2C3X approximating the
[AM]2R3X situation.
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Spectral analysis and iteration with DAISY yielded the following NMR parameter:

δi
1=2 A = A´ H 2.600 [ppm]
3=4 B = B´ H 1.889 [ppm]
5 C3 H 1.141 [ppm]
6 X P - [ppm]
νi
1=2 A = A´ H 936.00 [Hz]
3=4 B = B´ H 680.04 [Hz]
5 C3 H 410.76 [Hz]
6 X P - [Hz]
Jik
2
12 AA´ JHH -12.80 [Hz]
3
13 = 24 AB = A´B´ JHH 10.34 [Hz]
3
14 = 23 AB´ = A´B JHH 5.33 [Hz]
4
15 = 25 AC = AĆ JHH 0.01 [Hz]
2
16 = 26 AX = A´X JPH -14.64 [Hz]
2
34 BB´ JHH -14.04 [Hz]
3
35 = 45 BC = BĆ JHH 7.40 [Hz]
3
36 = 46 BX = B´X JPH 17.84 [Hz]
4
56 CX JPH 2.35 [Hz]
HWB global global 0.3 [Hz]
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1 31
Part I: Simulated Phosphorous Decoupled 360 MHz H{ P} NMR Spectra
980 970 960 950 940 930 920 910 900

(Hz)
980 970 960 950 940 930 920 910 900

(Hz)
Figure 488 : H{ P} NMR spectrum of CH3CH2CH2P(O)Cl2. α-Methylene region.

1 31
720 710 700 690 680 670 660 650 640

(Hz)
720 710 700 690 680 670 660 650 640

(Hz)
Figure 489 : H{ P} NMR spectrum of CH3CH2CH2P(O)Cl2. β -Methylene region.

1 31
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450 440 430 420 410 400 390 380 370

(Hz)
Figure 490 : H{ P} NMR spectrum of CH3CH2CH2P(O)Cl2. γ-Methyl region.

1 31
Comments to NMR Spectral Analysis for the n-Propyl Skeleton in CH3CH2CH2P(O)Cl2
This [AB]2C3 problem is solved by [AM]2R3 approximation:

4 3
a) Start at the methyl region, the R3 part. JAR = JHH is negligibly small or zero. JMR = JHH and
νR are directly extracted from the triplet structure. Remember for vicinal couplings:
3
sign( JHH) = positive.
b) Then to the α-methylene region, the A part. Since JAR = JHH is negligibly small or zero, we
4
see the A part of an [AB]2 model approximating the [AX]2 situation discussed in a preceding
chapter on 4-spin systems. Find N = JAB + JAB´ and νA (center of N-lines) directly from the
spectrum. The remaining 6 lines (inside the N-lines) plus two weak outer lines form the K-
and M-sub-spectra, where K = JAA´ + JBB´ and M = JAA´ - JBB´. Since both JAA´ and JBB´
2
correspond to geminal couplings JHH: K > M . JAA´ = (K + M)/2. JBB´ = (K - M)/2. Remember
2
for geminal couplings: sign( JHH) = negative.
c) The center of the β-methylene region approximates νB. Further analysis is not needed. All
coupling constants for [AB]2C3 were determined from regions A- and C-regions.
d) Start iteration with DAISY using data extracted under a) to c). DAISY will converge rapidly
to yield final optimized parameters.
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1
Part II: Simulated 360 MHz H NMR Spectra
980 960 940 920 900

(Hz)
980 960 940 920 900

(Hz)
Figure 491 : H NMR spectrum of CH3CH2CH2P(O)Cl2. α-Methylene region.

1
720 700 680 660 640

(Hz)
720 700 680 660 640

(H z)
Figure 492 : H NMR spectrum of CH3CH2CH2P(O)Cl2. β-Methylene region.

1
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460 440 420 400 380 360

(Hz)
Figure 493 : H NMR spectrum of CH3CH2CH2P(O)Cl2. γ-Methyl region.

1
n
Coupling Constants JPH in CH3CH2CH2P(O)Cl2
n
Coupling sign( JPH) Corresponds to the Doublet Splitting in
γ-methyl region
4
a JMX = JPH positive
α-methylene region
2
b JAX = JPH negative
β-methylene region
3
c JBX = JPH positive
Data from: M. Engelhardt; PhD Thesis 1986, Heinrich-Heine-University, Düsseldorf.
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12.1.3 Exercise: n-Propylfluoride CH3CH2CH2F
1
Hooper, Sheppard, and Woodman described attempts to analyze and iterate the 100 MHz H NMR
spectrum of CH3CH2CH2F using the frequency based iterators LAOCOON II and UEANMR II.
Partial solutions were obtained where parameters L and M for this [AB]2C3X system might be:
a) L = 0 Hz (corresponding to A2B2C3X) or
b) L = 1 Hz and M = 2 Hz (the [AB]2C3X case).
1
100 MHz H NMR Parameter of CH3CH2CH2F
Parameter Type [AB]2C3X A2B2C3X
δi Data Data
1=2 A, A´ 4.36 4.36 [ppm]
3=4 B, B´ 1.68 1.68 [ppm]
5 C3 0.97 0.97 [ppm]
6 X - - [ppm]
νi
1=2 A, A´ 436.00 436.00 [Hz]
3=4 B, B´ 168.00 168.00 [Hz]
5 C3 97.00 97.00 [Hz]
6 X - - [Hz]
Jik
12 AA´ -12* - [Hz]
13 = 24 AB 7.40* 6.90 [Hz]
14 = 23 AB´ 6.40* 6.90 [Hz]
15 = 25 AC -0.12 -0.12 [Hz]
16 = 26 AX 47.35 47.35 [Hz]
34 BB´ -14* - [Hz]
35 = 45 BC 7.45 7.45 [Hz]
36 = 46 BX 23.55 23.55 [Hz]
56 CX 0.38 0.38 [Hz]
N AB+AB´ 13.8 13.8 [Hz]
L AB-AB´ 1.0 0 [Hz]
K AA´+BB´ -26* - [Hz]
M AA´-BB´ 2 - [Hz]
HWB global 0.2* 0.2* [Hz]
Original data from: D. L. Hooper, N. Sheppard, C. M. Woodman; J. Mol. Spect. 24, 277-286
(1967). *) Data inserted for subsequent [AB]2C3X simulation:
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450 400 350 300 250 200 150 100

(Hz)
1
Figure 494 : A good approximation for the 100 MHz H NMR spectrum of CH3CH2CH2F.
This interesting paper by Hooper, Sheppard, and Woodman clearly indicates the limitations in
frequency based iterations (LAOCOON type programs). Line shape iteration might lead to an
1
optimized parameter set. Re-measurement of H NMR and iteration by DAISY for CH3CH2CH2F are
suggested.
12.2 i-Propyl Compounds
12.2.1 AB6 and A6B Systems in 1H NMR Spectra of

(CH3)2CH-SiR3 (R = Cl, Me)
1
Isopropyl groups attached in non-chiral units give rise to AB6 to A6B H NMR spectra. Substituent
effects determine the spectral character as indicated by the numerical value of the “spectral
relation” r defined below.
νH (CH) − νH (CH3 )
[1] r = 3
JHH
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Two examples will be studied: AB6 in (CH3)2CH-SiCl3 and A6B in (CH3)2CH-SiMe3:
1.50 1.45 1.40 1.35 1.30 1.25 1.20

(ppm)
Figure 495 : AB6 in (CH3)2CH-SiCl3 at 500 MHz
0.95 0.90 0.85 0.80 0.75 0.70 0.65

(ppm)
Figure 496 : A6B in (CH3)2CH-SiMe3 at 500 MHz
Corresponding data are listed below:
1
H NMR Data for (CH3)2CH-SiR3
δH(CH) δH(CH3) δH(Me)

3
System R JHH r
AB6 Cl 1.481 A 1.191 B6 7.35 3.946 -
A6B Me 0.673 B 0.924 A6 7.44 -3.374 -0.057
Data from:
1) G. Hägele, W. Peters, M. Weidenbruch; Ber. Bunsen Ges. Phys. Chem. 78, 781-785 (1974).
2) M. Weidenbruch, W. Schiffer, G. Hägele, W. Peters; J. Org. Met. Chem. 90, 145-157 (1975).
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General Remarks on the Composite Particle Analysis of ABn Systems
A group of n spins I = ½ with properties νi = νk and Jim = Jkm (i = 1 to (n-1), k = I to n) for all m
external spins is magnetical equivalent and forms a composite particle with total spin Fmax = n/2.
This group can be divided into n/2+1 sub-groups characterized by F = 0, 1, 2 to Fmax if n is even or
(n+1)/2 sub-groups. If n is odd than F = 1/2, 3/2 to Fmax.
Sub-groups are affiliated with statistical weights g(n,F) following
n!(2F + 1)
[2] g(n,F) =
n n
( − F)!( + F + 1)!
2 2
Each sub-group gives rise to an individual sub-spectrum.
Application to AB6
For the AB6 case of (CH3)2CH-SiCl3 the doublet state D of the A-proton combines with the singlet,
triplet, quintet and septet states of the B6 composite particle to form four independent sub-spectra
due to DS, DT, DQt and DSp with F values 0, 1, 2, and 3 for sub-groups in B6. Corresponding
statistical weights are 5 (DS), 9 (DT), 5(DQt), and 1 (DSp).
The total number of lines for the AB6 spectrum is classified in the following Table:
Number of Transitions in AB6
A B C
DS 1 - -
DT 3 4 1
DQt 5 8 3
DSp 7 12 5
Sum 16 24 9
A: A-lines. B: B-line. C: Combination lines.
Note: It is NOT necessary to analyze the total AB6 spectrum! From the A part in DS (and in DT)
parameter νA and from the B6 part approximations for νB and JAB are obtained.
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The AB6 Example from (CH3)2CH-SiCl3 at 500 MHz
The resonance frequency νA is readily accessible as shown in graphics and formulae below:
Figure 497 : (CH3)2CH-SiCl3. A part. Find → νA line indicated by black arrow. Sub-spectra: DS, DT, DQT,
and DSp.
The A Part
16 A-lines may be resolved if good resolution is achieved by low spectral half width and good
shimming. It is not necessary to analyze all 16 transitions frequencies. It suffices to inspect 4 lines
indicated as a1, a3, a5, and a8. With variables
[3] ∆ = ν A − νB
1
[4] z= ( ν A + νB )
2
1 2 9
[5] C=1 ∆ + ∆J + J2
2 4
1 2 9
[6] C=
2 ∆ − ∆J + J2
2 4
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explicit algebraic expressions are derived for the A part:
State Line Frequency

DS a1 νA
3
DT a3 z + J + C1
4
DT a5 νB + C1 + C2
3
DT a8 z − J + C2
4
The resonance frequency νA is accessible from:
[7] νa1 =ν A
or - for a check - from:
[8] νa3 + νa8 − νa5 =νA
The B6 Part
600 590
(Hz)
Figure 498 : (CH3)2CH-SiCl3 B6 part.
Find an approximation for νB from “center” and for JAB from “splitting” of “doublet”. 24 B6-transitions
overlap to form effectively this apparent “doublet”. Refine parameters νA, νB and JAB by iteration - if
high accuracy of results is needed.
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Additional Remarks to AB6, AX6, AB3C3 and AM3X3
a) The limiting AX6 case: At higher fields, with increasing spectral relation r, the AB6 case
approximates AX6. Then the A part consists of a septet with lines situated at νA+(3-i) JAX
(i = 0 to 6) and intensities 1:6:15:20:15:6:1. The X6 part is represented by a doublet at νX ±

0.5 JAX with intensities 192:192.
b) If the (CH3)2CH- is attached to a chiral unit the geminal methyl pair might exhibit non-
4
equivalence and an AB3C3 to AM3X3 system is formed. Couplings JHH (JBC or JMX) are
small to zero.
The A6B Case in (CH3)2CH-SiMe3 at 500 MHz
(CH3)2CH-SiCl3 yielded an AB6 spectrum but (CH3)2CH-SiMe3 gives rise to an A6B system as
shown below.
470 460 450

(Hz)
Figure 499 : (CH3)2CH-SiMe3 A6 part
360 350 340 330 320 310

(Hz)
Figure 500 : (CH3)2CH-SiMe3 B part
Exercise: Perform the A6B analysis in analogy to the AB6.
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12.2.2 The AB6X System in (CH3)2CHP(O)Cl2
Isopropylphosphonic acid dichloride gives rise to an AB6X spin system at lower fields and will reach
first order situation with AM6X at ≥ 360 MHz. Decoupling the phosphorous by 1H{31P} NMR leads
to AB6 and AM6 resp..
Parameter Type Data

δH(A) (CH3)2CHP(O)Cl2 2.70 [ppm]
δH(B6) (CH3)2CHP(O)Cl2 1.42 [ppm]

3
JAB JHH 7.01 [Hz]
2
JAX JPH -12.28 [Hz]
3
JBX JPH 28.07 [Hz]
Data from: M. Engelhardt; PhD Thesis 1986, Heinrich-Heine-University, Düsseldorf.
At higher fields a doublet of septet is observed for the α-methine proton in CHP while the β-methyl
31
group appears as a doublet of doublet. (And the P NMR spectrum reveals a first order doublet of
septets). Hence plots of simulated spectra are not requested for this case. Simulate the 90 MHz
1 1 31 1 31
and the 360 MHz H and H{ P} NMR spectra. The 90 MHz H{ P} NMR spectrum will reveal a
nice AB6 pattern with a spectral relation of rAB = 16.4, resembling the spectrum of (CH3)2CHSiCl3
shown above.
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1
12.2.3 H NMR Spectra of Further Alkanes
Schrumpf et al. presented detailed studies on n-butyl, s-butyl-, and n-pentyl-derivatives.

Partially deuterated isotopomers were used to obtain partial solutions for those complex NMR
spectra.
Compounds System Substituent R Ref.

CH3-CH2-CH2-CH2-R [ABC]2D3 Cl a
CH3-CH2-CH2-CD2-R [AB]2C3 OCH3, Cl, Br, I a
CD3-CH2-CH2-CH2-R [ABC]2 Cl, Br, I a
CH3-CHD-CHD-CH2-R ABC2D3 OCH3, Cl, Br, I a
CH3-CH2-CHR-CH3 [ABCD]2E3 Cl, Br, I b
CH3-CH2-CH2-CH2-CH2-R [ABCD]2E3 OH, Cl, Br, I c
CH3-CH2-CH2-CD2-CH2-R [ACD]2E3 OH, Cl, Br, I c
CH3-CH2-CD2-CH2-CH2-R [ABD]2E3 OH, Cl, Br, I c
CH3-CD2-CH2-CH2-CH2-R [ABC]2E3 OH, Cl, Br, I c
If you need to look closer in problems listed above read the papers from Schrumpf et al..
References
a) G. Schrumpf, A. Schlenker; Chem. Ber. 111, 1126-1135 (2978)

b) G. Schrumpf; Chem. Ber. 106, 246-265 (1973)
c) G. Schrumpf, A. W. Klein; Chem. Ber. 106, 266-279 (1973)
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Concluding Remarks on 1H and 1H{31P} NMR Spectra of n-, s-, i-, and t-Butyl-P(O)Cl2
1
A systematic contribution to spectral analysis of H NMR spectra of alkyl phosphorous RP(O)Cl2
was made by M. Engelhardt, who reported results from four isomeric structures, the n-, s-, i-, and t-
butyl compounds using spin enumerations shown below:
H H H 5 3 1 C B A
H 3C C C C P(O)Cl2 7 8 D3 X
H H H 6 4 2 C´ B´ A´
CH3-CH2-CH2-CH2-P(O)Cl2 n-Butyl [ABC]2D3X [ABC]2M3X
H H 3 1 C A
H 3C C C P(O)Cl2 5 6 E3 X
H CH3 2 4 B D3
CH3-CH2-CH(CH3)-P(O)Cl2 s-Butyl ABCD3E3X ABCM3R3X
CH3 H 3 1
H C C P(O)Cl2 2 4 B C6 A2 X
CH3 H 3 1
(CH3)2CH-CH2-P(O)Cl2 i-Butyl A2BC6X A2BM6X
CH3 1
H 3C C P(O)Cl2 1 2 A9 X
CH3 1
(CH3)3C-P(O)Cl2 t-Butyl A9X
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1
360 MHz Simulations of H NMR Spectra from RP(O)Cl2
CH3CH2CH2CH2P(O)Cl2
2.6 2.4 2.2 2.0 1.8 1.6 1.4 1.2 1.0

(ppm)
1
Figure 501 : 360 MHz H NMR simulation of RP(O)Cl2: R = n-Butyl.
CH3CH2CH(CH3)P(O)Cl2
2.4 2.2 2.0 1.8 1.6 1.4 1.2

(ppm)
1
Figure 502 : 360 MHz H NMR simulation of RP(O)Cl2: R = s-Butyl.
(CH3)2CHCH2P(O)Cl2
2.6 2.4 2.2 2.0 1.8 1.6 1.4 1.2

(ppm)
1
Figure 503 : 360 MHz H NMR simulation of RP(O)Cl2: R = i-Butyl.
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1
360 MHz H NMR Data for n-Butyl-P(O)Cl2 - [ABC]2D3X
H H H 5 3 1 C B A
H 3C C C C P(O)Cl2 7 8 D3 X
H H H 6 4 2 C´ B´ A´
H3CH2CH2CH2P(O)Cl2
δi [ppm]
1=2 A H 2.611
3=4 B H 1.822
5=6 C H 1.529
7 D3 H 0.982
8 X P -
νi νi [Hz]
1=2 A H 939.96
3=4 B H 655.92
5=6 C H 550.44
7 D3 H 353.52
8 X P -
Jik Jik
2
12 AA´ JHH -14.91
3
13=24 AB JHH 10.93
3
14=23 AB´ JHH 5.05
4
15=26 AC JHH -0.30
4
16=25 AC´ JHH -0.16
5
17=27 AD JHH 0
2
18=28 AX JPH -14.91
2
34 BB´ JHH -13.47
3
35=46 BC JHH 8.95
3
36=45 BC´ JHH 5.97
4
37=47 BD JHH 0
3
38=48 BX JPH 16.50
2
56 CC´ JHH -13.45
3
57=67 CD JHH 7.30
4
58=68 CX JPH 0
5
78 DX JPH 0
HWB global 0.30
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1
360 MHz H NMR Simulation for s-Butyl-P(O)Cl2 - ABCD3E3X
H H 3 1 C A
H 3C C C P(O)Cl2 5 6 E3 X
H CH3 2 4 B D3
CH3CH2CH(CH3)P(O)Cl2
δi [ppm]
1 A H 2.471
2 B H 2.105
3 C H 1.590
4 D3 H 1.408
5 E3 H 1.118
6 X P -
νi [Hz]
1 A H 889.56
2 B H 757.80
3 C H 572.40
4 D3 H 506.88
5 E3 H 402.48
6 X P -
Jik
3
12 AB JHH 9.43
3
13 AC JHH 3.90
4
14 AE JHH 0.00
3
15 AD JHH 6.96
2
16 AX JPH -13.31
2
23 BC JHH -14.14
3
24 BE JHH 7.45
4
25 BD JHH 0
3
26 BX JPH 13.90
3
34 CE JHH 7.46
4
35 CD JHH 0
3
36 CX JPH 19.90
5
45 DE JHH 0
4
46 EX JPH 0.95
3
56 DX JPH 28.92
HWB global 0.30
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1
360 MHz H NMR Simulation for i-Butyl-P(O)Cl2 - A2BC6X
CH3 H 3 1
H C C P(O)Cl2 2 4 B C6 A2 X
CH3 H 3 1
(CH3)2CHCH2P(O)Cl2

δi [ppm]
1 A H 2.563
2 B H 2.370
3 C H 1.174
4 X P -
νi [Hz]
1 A H 922.68
2 B H 853.20
3 C H 422.64
4 X P -
Jik
3
12 AB JHH 6.71
4
13 AC JHH 0
2
14 AX JPH -14.53
3
23 BC JHH 6.62
3
24 BX JPH 17.33
4
34 CX JPH 1.59
HWB global 0.30
Data for n-, s-, and i-BuP(O)Cl2 from: M. Engelhardt; PhD Thesis, 1986, Heinrich-Heine-
1
University, Düsseldorf. Thanks are due to D. Leibfritz and M. Feigel, Bremen, for 360 MHz H NMR
spectra.
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1
H NMR Data for t-Butyl-P(O)Cl2 - A9X
CH3 1
H 3C C P(O)Cl2 1 2 A9 X
CH3 1
Trivial doublet at δH(CH3) = 1.41 ppm. 3JPH = 28 Hz.
Data for t-ButylP(O)Cl2 from: R. Schmutzler, G. S. Reddy; Z. f. Naturforsch. 20b, 832 (1965)
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Five Spins: H-F-Aliphatic Compounds
13 Five to Six Spins: H-F-Aliphatic

Compounds
13.1 ABCRX System in 1,2-Difluoropropionic Acid Ethylester

CH2F-CHF-COOEt
Gas phase fluorination of C2H5COF yielded a mixture of fluorinated propionylfluorides

1)
C2H5-iFiCOF (i = 1-4) which were converted into ethylesters C2H5-iFiCOOEt . First order analysis
1 19 1)
based on H and F NMR spectra of corresponding 5-spin systems identified individual products
as listed below:
i Compound Analysis i Compound Analysis

1 CH3CHFCOOEt AR3X 3 CH2FCF2COOEt A2R2X *
1 CH2FCH2COOEt A2R2X * 3 CHF2CHFCOOEt AHKRX **
2 CH3CF2COOEt A3X2 3 CF3CH2COOEt A2X3
2 CH2FCHFCOOEt ABCRX 4 CHF2CF2COOEt AR2X2 *
2 CHF2CH2COOEt AR2X2 * 4 CF3CHFCOOEt ARX3
*) treated as deceptively simple. **) simplified first order.
Deeper inspections of NMR spectra revealed that 1,2-difluoropropionic acid ethylester

2)
CH2F-CHF-COOEt exhibited a second order spin system of ABCXY to ABCRX type . Iterative
1 19
treatment of high precision H and F NMR spectra yielded parameters shown below:
H H 2 3 B A
H C C COOEt 1 C
F F 5 4 X M
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Chemical Shifts of CH2F-CHF-COOEt
δi δi δi [ppm]
1 C H 4.7568
2 B H 4.7647
3 A H 5.1127
4 R F -36.0570
5 X F -77.2417
Coupling Constants of CH2F-CHF-COOEt
Jik Type Type [Hz]

2
12 BC JHH -11.30
3
13 AC JHH 4.11
3
14 CR JFH 30.25
3
15 CX JFH 46.59
3
23 AB JHH 1.92
3
24 BR JFH 21.30
2
25 BX JFH 47.94
2
34 AR JFH 47.31
3
35 AX JFH 28.42
3
45 RX JFF -11.16
Solvent: CCl4. Concentration: 75%. Internal references: TMS and C6F6.
1 19
For didactical purposes 500 MHz H and 470 MHz F NMR spectra were simulated using a global
line width of 0.5 Hz.
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5.20 5.10 5.00 4.90 4.80 4.70

(ppm)
1
Figure 504 : 500 MHz H NMR spectrum – ABC part
-35.90 -36.00 -36.10 -36.20

(ppm)
19
Figure 505 : 470 MHz F NMR spectrum – R part
-68.90 -69.00 -69.10

(ppm)
19
Figure 506 : 470 MHz F NMR spectrum – X part
19
Center and repeated spacings of the F NMR spectrum provide good approximations for δF, νF,
n n 1
JFH and JFF. But the evaluation of the H NMR spectrum is more laborious.
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1 19
Hence for a start a fluorine decoupled H{ F} NMR spectrum is recommended, which appears with
ABC features approximating AXY (compare chapter 7.2):
5.10 5.00 4.90 4.80 4.70

(ppm)
5.10 5.00 4.90 4.80 4.70

(ppm)
1 19
Figure 507 : 500 MHz H{ F} NMR spectrum. Lower trace is y-expanded.
19 1
The proton decoupled 470 MHz F{ H } NMR spectrum is primitive and hence not shown here. It
appears as a simple RX type spectrum with doublets centered at δF(FR) and δF(FX) exhibiting
3
directly the absolute value of JRX = JFF.
Parameters obtained above would suffice for a successful iteration using TopSpin / DAISY.
Exercise: Simulate NMR spectra varying spectrometer frequencies and study variation of spectral
2) 1 19
appearance. The original study used 100 MHz H and 84.67 MHz F NMR.
References
1. J. A. Brocks, R. Kosfeld, P. Sartori, M. Schmeißer; Chem. Ber. 103, 1692-1700 (1970)

2. G. Hägele, R. K. Harris, P. Sartori; Org. Magn. Res. 3, 463-473 (1971)
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Remarks
2) 3
Ref. discusses intramolecular rotation and substituent effects on JFH. Spectral patterns are
influenced by solvent, concentration and temperature. Proton NMR data are compared for 3- and
4-spin systems of CH2Cl-CHCl-COOEt, CH2Br-CHBr-COOEt, CH2Br-CHF-COOEt, CH2F-CHBr-
COOEt.
13.2 6-Spin Systems from Fluorinated Ethanes C2H6-nFn and

Acetones C3H6-nOFn:
Fluorinated ethanes C2H6-nFn have attracted considerable attention in spectral analysis involving
effects due to intra molecular rotation. Looking back in our manuscript will help to understand the
1 19
H and F NMR spectra of a majority of the following compounds.
n Ref. Compound System n Ref. Compound System

0 CH3-CH3 A6 6 CF3-CF3 X6
1 CH3-CH2F A2B3X 5 CF3-CHF2 AM3X2
2 CH3-CHF2 AM3X 4 CF3-CH2F A2M3X
2 1 CH2F-CH2F [[A]2X]2 4 2 CHF2-CHF2 [A[X]2]2
3 CH3-CF3 A3X3 3 3 CH2F-CHF2 A[MR]2X
Interesting new aspects for spectral analysis were introduced with studies on compounds
CH2F-CH2F ([[A]2X]2), CHF2-CHF2 ([A[X]2]2), and CH2F-CHF2 (A[MR]2X).
If you wish to learn more about those systems then read:
1. B. Pedersen, P. Klæboe, T. Torgrimsen; Acta Chem. Scand. 25, 2367-2368 (1971). b) R.

J. Abraham, R. H. Kemp; J. Chem. Soc. (B) 1971, 1240-1245. c) S. Watanabe, I. Ando; J.
Mol. Struct. 104, 155-161 (1983).
2. L. Cavalli, R, J, Abraham; Mol. Phys. 19, 265 (1970).
3. R. J. Abraham, R. H. Kemp; J. Chem. Soc. (B) 1971, 1240-1245. b) R. R. Dean, J. Lee;
Trans. Faraday Soc. 64, 1409 (1968).
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Analogous Spin Systems were Derived from Fluorinated Acetones C3H6-nOFn:
n Ref. n Ref.
0 CH3-CO-CH3 A6 6 CF3-CO-CF3 X6
1 1 CH3-CO-CH2F A2M3X 5 2 CF3-CO-CHF2 AM3X2
2 1 CH3-CO-CHF2 AM3X2 4 2 CF3-CO-CH2F A2M3X
2 3 CH2F-CO-CH2F [[A]2X]2 4 3 CHF2-CO-CHF2 [A[X]2]2
3 2 CH3-CO-CF3 A3X3 3 CH2F-CO-CHF2 A[MR]2X
NMR data were reported in:
1. B. L. Shapiro, C. K. Tseng, M. D. Johnston, Jr.; J. Magn. Res. 10, 65-73 (1973)

2. B. L. Shapiro, H.-L. Lin, M. D. Johnston, Jr.; J. Magn. Res. 9, 305-325 (1973)
3. CH2F-CO-CH2F and CHF2-CO-CHF2: B. L. Shapiro, W. A. Thomas, J. L. McClanahan,
M. D. Johnston; J. Magn. Res. 11, 355-366 (1973).
Of particular interest were the symmetrically substituted acetones CH2F-CO-CH2F and CHF2-CO-
CHF2 which give rise to interesting [[A]2X]2 and [A[X]2]2 spectra.
Exercise: Simulate, compare and discuss spectra from

a) CH2F-CH2F / CH2F-CO-CH2F and
b) CHF2-CHF2 / CHF2-CO-CHF2.
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Five to Six Spins: Propene and Halopropenes
14 Five to Six Spins: Propene and

Halopropenes
14.1 Propene and Chloropropenes
1
At low fields propene 1 gives rise to rather complex H NMR spectra of ABCD3 type. Raising the
field simplifies spectra - for ≥ 300 MHz AMRX3 spectra are observed. Due to the strong substituent
effect of chlorine, the three isomers 2 - 4 of chloropropene exhibit simple ABX3 patterns, even at
60 MHz.
Spin Systems
Compound 1 2 3 4
Spin system at low field ABCD3 ABC3 ABC3 ABC3
Spin system at high field ABCX3 ABX3 ABX3 ABX3
1
H NMR Data of Propenes 1 - 4
Parameter Type Data 1 Data 2 Data 3 Data 4

δ1 δH 5.73 - 5.8417 5.7433 [ppm]
δ2 δH 4.88 5.0550 - 5.9683 [ppm]
δ3 δH 4.96 5.0633 5.8950 - [ppm]
δ4 δH 1.66 2.0700 1.6467 1.7117 [ppm]
3
J12 JHH (cis) 10.02 - - 7.0 [Hz]
3
J13 JHH (trans) 16.81 - 13.2 - [Hz]
3
J14 JHH (g) 6.40 - 6.9 6.6 [Hz]
2
J23 JHH (gem) 2.08 -1.3 - - [Hz]
4
J24 JHH (t) -1.33 -0.7 - -1.7 [Hz]
4
J34 JHH (c) -1.75 -1.2 -1.7 - [Hz]
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Exercise: Simulate and reanalyze spectra. For details read:

a) Bothner-By, C. Naar-Colin; J. Amer. Chem. Soc. 83, 231 (1961).
b) M. Y. DeWolf and J. B. Baldeschwieler; J. Mol. Spec. 13, 344-359 (1964).
Fluoropropenes CH2=CH-CH3-nFn
H CH2F H CHF2 H CF3 3 4
C C C C C C
H H H H H H 2 1
ABCD2X ABCDX2 ABCX3 low field

ABCM2X ABCMX2 ABCX3 high field
Parameter Type CH2=CH-CH2F CH2=CH-CHF2 CH2=CH-CF3

1 2 3
δ1 δH 4.1145 5.9138 5.9030 [ppm]
δ2 δH 5.0563 5.4570 5.5530 [ppm]
δ3 δH 5.2397 5.5687 5.8555 [ppm]
δ4 δH 4.6898 5.9753 - [ppm]

3
J12 JHH(cis) 10.64 10.82 11.12 [Hz]
3
J13 JHH(trans) 17.21 17.52 17.47 [Hz]
3
J14 JHH 5.31 5.33 - [Hz]
3
J15 JFH 14.53 8.63 6.28 [Hz]
2
J23 JHH 1.54 0.67 0.18 [Hz]
4
J24 JHH(trans) -1.27 -0.79 - [Hz]
4
J25 JFH(trans) -0.89 -0.14 +0.03 [Hz]
4
J34 JHH(cis) -1.63 -0.82 - [Hz]
4
J35 JFH(cis) -4.32 -3.66 -2.22 [Hz]
2
J45 JFH 46.75 55.90 - [Hz]
1 19
NMR data from analysis of 60 MHz H and 56.5 MHz F NMR. Neat samples with 0.5 to 1.0%
TMS as internal reference. Chemicals shift δ5 = δF and resonance frequency ν5 = νF not quoted.
Data from: A. A. Bothner-By, S. Castellano, H. Günther; J. Amer. Chem. Soc. 87, 2439-2442
(1965).
Exercise: Simulate and reanalyze the original 60 MHz spectra and compare 500 MHz simulations.
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14.2 AM3X Spectra of Cis- and Trans-Isomers of

1-Chloro-2-fluoro-prop-(1)-ene
H F Cl F
C C C C
Cl CH3 H CH3
1 19
Cis- and trans-isomers of 1-chloro-2-fluoro-prop-(1)-ene give rise to first order H and F NMR
spectra exhibiting the simple AM3X character.
This is true even for very low fields, where (in a historical, pioneering experiment) the magnetic
1
field strength of the spectrometer was adjusted for H NMR at 40 MHz and in a separate
19
experiment for F NMR 40 MHz as well.
40 MHz Data of CH3-CF=CHCl
cis- CH3-CF=CHCl trans- CH3-CF=CHCl

Parameter Type Data Type Data
δ1 δH (CH) A 5.86 δH (CH) A 5.31
δ2 δH (CH3) M3 1.99 δH (CH3) M3 1.92
δ3 δF (F) X 12.66 δF (F) X 10.18

4 4
J12 JHH (trans) 1.14 JHH (cis) 1.26
3 3
J13 JFH (cis) 10.8 JFH (trans) 24.2
3 3
J23 JFH (gem) 16.85 JFH (gem) 16.3
Data from: C. A. Reilly; J. Chem. Phys. 37, 456-457 (1962)
1 19
The spectral habitus of H and F NMR spectra is primitive. The A- (CH) and the X- (CF) parts
reveal specific doublets of quartets; while the M3- (CH3) parts simply consist of doublets of
doublets.
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14.3 ABC3, ABX3, AMX3 Spectra of

2-Chloro-1,1,3,3,3-pentafluoro-prop-(1)-ene
F1 Cl
C C
F2 CF3
19
F NMR data of CF3-CCl=CF2
Parameter Type Data

δ1 δF (CF) B -6.2
δ2 δF (CF) A -5.9
δ3 δF (CF3) C3 -18.6
2
J12 JFF (gem) 16.65
4
J13 JFF (trans) 9.20
4
J23 JFF (cis) 23.83
19
The original 40 MHz F NMR spectrum (J. D. Swalen and C. A. Reilly; J. Chem. Phys. 34, 2122-
19
2129 (1961)) is an ABC3 case close to the ABX3 situation. Above 188.15 MHz F NMR reveals a
simpler ABX3 pattern: a doublet of doublets for the X3 part and the super-position of 4 ab sub-
spectra for the AB part. Above 282.15 MHz those 4 ab sub-spectra are well separated into A- and
B-regions approximating the limiting case of AMX3 at highest fields.
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-200 -220 -240 -260 -280

(Hz)
-700 -720 -740 -760 -780

(Hz)
19
Figure 508 : 40 MHz F NMR spectrum; upper: CF2 part (AB); lower: CF3 part (C3, X3). Red: N =
JAX+JBX.
Exercise: Simulate and reanalyze the 470.385 MHz AMX3 case.
CF2=CCl-CF3 is an excellent case to learn more about the general ABX3 case.
Start reading with:

a) V. J. Kowalewski, D. G. Kowalewski; J. Chem. Phys. 33, 1794-1798 (1960), where explicit
equations are given for transition frequencies and intensities of A, B, and X parts.
Then follow:
b) F. Hruska, D. W. McBride, T. Schaefer; Can. J. Chem. 45, 1081-1087 (1960).
c) J. A. Pople, T. Schaefer; Mol. Phys. 3, 547 (1960).
d) M. Y. DeWolf, J. D. Baldeschwieler; J. Mol. Spectr. 13, 344 (1964).
e) P. L. Corio, "Structure of High-Resolution NMR Spectra". Academic Press, New York-
London, 1966, p. 308-311.
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14.4 ABCD3, AMNX3, AMRX3 Spectra of Perfluoropropene
1 19
While the H NMR spectrum of CH2=CH-CH3 is rather complex, the F NMR spectrum of CF2=CF-
CF3 approximates the AMNR3 case, even at frequencies as low as 40 MHz.
F1 F3
C C
F2 CF3
19
F NMR data of CF3-CF=CF2
Parameter Type Data

δ1 δF (CF) C 11.6 [ppm]
δ2 δF (CF) B 25.1 [ppm]
δ3 δF (CF) A 110.6 [ppm]
δ4 δF (CF3) D3 -13.0 [ppm]

2
J12 JFF (gem) 60.0 [Hz]
3
J13 JFF (cis) 40.3 [Hz]
4
J14 JFF (trans) 8.7 [Hz]
3
J23 JFF (trans) 120.2 [Hz]
4
J24 JFF (cis) 22.0 [Hz]
3
J34 JFF (gem) 13.2 [Hz]
Data from: J. D. Swalen and C. A. Reilly; J. Chem. Phys. 34, 2122-2129 (1961)
4000 3000 2000 1000 0

(Hz)
19
Figure 509 : Total simulated 40 MHz F NMR spectrum of CF3-CF=CF2.
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4520 4480 4440 4400 4360 4320

(Hz) a
1120 1080 1040 1000 960 920 880

(Hz) b
560 520 480 440 400 360

(Hz)
c
-400 -440 -480 -520 -560 -600 -640

(Hz) d
19
Figure 510 : Expanded 40 MHz F NMR spectrum of CF3-CF=CF2; a) CF part (A), b) CF part (B), c) CF
part (C), d) CF3 part (D3).
Manual analysis suffices - conveniently supported by the Multiplet Tool in TopSpin.
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Five Spins: ABC3 to ABX3 Crotonic Acid Ethylester
15 Five Spins: ABC3 to ABX3

Crotonic Acid Ethylester
ABC3 to ABX3 Spectra from Trans- and Cis-crotonic Acid Derivatives
In the early days of NMR D. D. Kowalewski and D. G. Kowalewski described "Nuclear Magnetic
Resonance Spectra of the ABX3 Type: Field Dependences and Relative Signs of Spin-Spin-
Coupling Constants" Read: J. Chem. Phys. 33, 1794-1798 (1960).
1
Explicit equations for transition frequencies and intensities were given. H NMR spectra were
measured at 60, 40 and 25 MHz from trans- and cis-crotonic acid and corresponding ethylesters.
Their findings motivated us to a re-investigation using high field spectrometers and modern
computer based spectral evaluation as shown below.
1
H NMR spectra from three isomeric ethylesters of trans-crotonic acid, cis-crotonic acid and vinyl
acetic acid can be handled as two-fragment problems giving rise to ABX3, ABCM2 (olefinic, allylic)
and A2M3 (aliphatic) systems as shown below:
CH3 H H H H H
C C C C C C
H COO-CH2-CH3 CH3 COO-CH2-CH3 H CH2-COO-CH2-CH3
1 2 3
ABX3+A2X3 ABX3+A2X3 ABCM2+A2X3
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1
Exercise: The 400 MHz H NMR spectrum of a hitherto unknown ester (in CDCl3) was obtained
with integrals indicated below:
1
Figure 511 : 400 MHz H NMR spectrum of an unknown structure.
5 characteristic resonance signals are observed, where signals 1 and 2 belong to 2 individual
olefinic protons, while signal 4 is affiliated with 3 magnetically equivalent protons in a methyl group
attached to the olefinic system. Signals 3 and 5 are clearly attributed to the A2M3 system of the
ethoxy function.
Without deeper inspections we can exclude structure 3, the vinyl acetic acid ethylester. Hence two
alternatives are left over: the trans- and the cis-forms of crotonic acid ethylester 1 and 2. The
3
stereochemical analysis is straightforward using the significant olefinic coupling constants JHH
which are trans in 1 and cis in 2.
Using the following spin assignment:

3 2
CH3 H CH3 H
C C C C
H COO-CH2-CH3 H COO-CH2-CH3
1 1 2
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spectral analysis and iteration yielded:
7.0 6.0 5.0 4.0 3.0 2.0 1.0

(ppm )
Figure 512 : Upper: experimental. Middle: simulated. Lower: Difference of intensities (x10).
Fragment Parameter nH Type Data

1 1 1 δH 6.8870 [ppm]
1 2 1 δH 5.7585 [ppm]
1 3 3 δH 1.7922 [ppm]
3
1 12 JHH(trans) 15.55 [Hz]
3
1 13 JHH 6.99 [Hz]
4
1 23 JHH(cis) -1.87 [Hz]
1 1 HWB 0.95 [Hz]
1 2 HWB 0.98 [Hz]
1 3 HWB 1.18 [Hz]
2 1 2 δH 4.0942 [ppm]
2 2 3 δH 1.1963 [ppm]
3
2 12 JHH 7.18 [Hz]
2 1 and 2 HWB 1.29 [Hz]
3 3
Those experimental coupling constants J12 = 15.55 Hz ( JHH trans olefinic), J13 = 6.99 Hz ( JCH3-CH)
4
and J23 = -1.87 Hz ( JCH3-C-C-H) are consistent with structure 1 only, the trans crotonic acid
4
ethylester. Note: Sign of JHH(cis) is negative according to Kowalewski.
1
For completeness inspect the expanded 400 MHz H NMR spectra which have identical frequency
scales for all expansions, but intensities are not to scale.
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Fragment 1
6.98 6.96 6.94 6.92 6.90 6.88 6.86 6.84 6.82 6.80
(ppm)
Signal 1 H1
5.80 5.78 5.76 5.74 5.72 5 1.82 1.80 1.78 1.76

(ppm) (ppm)
Signal 2 H2 Signal 4 Methyl group 3
Figure 513 : Fragment 1 - the CH3-CH=CH- unit.
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Fragment 2
4.14 4.12 4.10 4.08 4.06 4.04 24 1.22 1.20 1.18 1.16
(ppm) (ppm)
Signal 3 Methylene group 1 Signal 5 Methyl group 2

Figure 514 : Fragment 2 - the CH3-CH3-O- unit.
Spectral edition and evaluation of parameters is more convenient with TopSpin:
1
Figure 515 : Spectrum, peak picking and integrals.
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A powerful method for deconvolution was implemented in TopSpin which is superior to the
preceding WIN-NMR version.
Deconvolution Graphics
Figure 516 : Upper: deconvolution. Lower: experimental.
The corresponding list of peaks from deconvolution may be used to start manual analysis.
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Five or Ten Spins: AMNCX, AMRXY, AHMRX – Allyl Glycidyl Ether
16 Five or Ten Spins: AMNCX, AMRXY,

AHMRX – Allyl Glycidyl Ether
Analysis and Iteration of the 500 MHz 1H NMR Spectrum of Allyl Glycidyl Ether
H H H H
H C C H
C C O C C
H H H O H
1E 1D 2D 2E
1B C C 2B
C C O C C
1C 1A 2C O 2A
fragment 1 fragment 2
allyl glycidyl
Spin Allyl Glycidyl

1 1A 2A
2 1B 2B
3 1C 2C
4 1D 2D
5 1E 2E
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Allyl Glycidyl
6.0 5.5 5.0 4.5 4.0 3.5 3.0

(ppm)
1
Figure 517 : 500 MHz H NMR spectrum of allyl glycidyl ether. Solvent: CDCl3.
1
The 500 MHz H NMR spectrum of allyl glycidyl ether results from two separate 5-spin systems.
Spectral analysis and iteration can be done separately for allyl and glycidyl groups. It is not
necessary to tackle the total spectrum as a 10 spin case and it is not efficient to iterate the total
spectrum using two 5 spin fragments. This is a fortuitous case, where iteration may be performed
effectively in isolated spectral parts as will be shown below.
The allyl part gives rise to an AMNXY spectrum approximating the AMRXY situation. The glycidyl
spectrum appears more primitive as simple first order case AHMRX. Using the Multiplet function in
TopSpin leads to starting values for the allyl glycidyl ether problem. For accuracy both 5 spin
spectra are iterated as full second order ABCDE cases.
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16.1 The Allyl Group
6.0 5.6 5.2 4.8 4.4 4.0

(ppm)
Figure 518 : Total spectrum. Upper: experimental. Lower: iterated.
Expanded Spectra
5.96 5.92 5.88

(ppm)
Figure 519 : A part of allyl group.
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5.32 5.28 5.24 5.20

(ppm)
B Part C Part
Figure 520 : B and C parts of allyl group.
4.08 4.04 4.00

(ppm)
D Part E Part
Figure 521 : D and E parts of allyl group.
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Remarks to Part D and Part E
The DE pattern resembles the AB part of an ABMX2 system: basically we see doublets of triplets of
an ab sub-spectrum. Calculate centers 1 to 4 as shown below.
3
2
4
1
4.08 4.06 4.04 4.02 4.00

(ppm)
Figure 522 : Simplification for D and E parts of allyl group.
Then perform AB type analysis using frequencies 1 to 4 to obtain resonance frequencies and
chemical shifts of spins D and E and in addition the coupling constant JAB.
Results from ABCDE Iteration
First frequency point 3005.13

Last frequency point 1955.53
Number of points 10869
Hz/Point 0.097
rms 1.317
R-Factor ( % ) 1.427
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Parameter Type Data

Chemical shifts [ppm]
δA δH 5.9152
δB δH 5.2933
δC δH 5.2001
δD δH 4.0682
δE δH 4.0305
Resonance frequencies [Hz]
νA νH 2957.61
νB νH 2646.63
νC νH 2600.05
νD νH 2034.11
νE νH 2015.25
Coupling constants [Hz]
3
JAB JHH trans 17.27
3
JAC JHH cis 10.38
3
JAD JHH 5.60
3
JAE JHH 5.71
2
JBC JHH -1.76
4
JBD JHH cis -1.61
4
JBE JHH cis -1.60
4
JCD JHH trans -1.53
4
JCE JHH trans 1.51
2
JDE JHH -12.76
Line width [Hz]
HWBA HWBH 0.90
HWBB HWBH 0.76
HWBC HWBH 0.77
HWBD HWBH 0.73
HWBE HWBH 0.73
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16.2 The Glycidyl Group
3.8 3.6 3.4 3.2 3.0 2.8 2.6

(ppm)
Figure 523 : Total spectrum of glycidyl group
3.74 3.72 3.70 3.44 3.42 3.40 3

(ppm) (ppm)
A part B part
Figure 524 : A and B parts of glycidyl group.
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3.18 3.16 3.14

(ppm)
Figure 525 : C part of glycidyl group.
2.82 2.80 2.78 2.64 2.62 2.60

(ppm) (ppm)
D part E part
Figure 526 : D- and E parts of glycidyl group.
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Results from ABCDE Iteration
First frequency point 1898.17

Last frequency point 1260.39
Number of points 6605
Hz/Point 0.097
Iteration 33 rms 1.536
R-Factor ( % ) 1.458
Parameter Type Data

Chemical shifts [ppm]
δA δH 3.7238
δB δH 3.4177
δC δH 3.1625
δD δH 2.8015
δE δH 2.6193
Resonance frequencies [ppm]
νA νH 1861.88
νB νH 1708.87
νC νH 1581.27
νD νH 1400.76
νE νH 1309.63
Coupling constants [ppm]
2
JAB JHH -11.47
3
JAC JHH cis 3.14
4
JAD JHH 0.25
4
JAE JHH -0.24
3
JBC JHH trans 5.78
4
JBD JHH -0.27
4
JBE JHH -0.39
3
JCD JHH 4.15
3
JCE JHH 2.69
2
JDE JHH -5.06
Line width [ppm]
HWBA HWBH 0.80
HWBB HWBH 0.84
HWBC HWBH 0.90
HWBD HWBH 0.75
HWBE HWBH 0.74
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709
Remarks on Line Width and Resolution
Numerical data for line widths HWBE of proton HE in the allyl group and HWBC of proton HC in the
glycidyl group do not iterate well. Hence suitable data were obtained by repeated simulations.
This experimental spectrum is characterized by nuclear specific spectral line widths between 0.7 to
0.9 Hz and by a digital resolution between 7 to 9 points / line width. For line shape iteration a digital
resolution of ≥ 15 points / line width is recommended.
n
No evidence is obtained for coupling across the C-O-C bond, e.g. JHH (n = 4-8).
Suggestion: Check for cross oxygen long range couplings by HH-COSY spectra.
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Five to Six-Spins: ABCDE and ABCDEX – Butadienes
17 Five to Six Spins: ABCDE and

ABCDEX – Butadienes
17.1 ABCDE Spectra of Three Isomeric Methoxybutadienes
1
Isomeric methoxybutadienes 1 to 3 give rise to H NMR spectra of ABCDE type characterized by
stereo specific data. In addition singlets are observed for the methoxy groups.
1 3
C C 5
2 C C
4 6
CH3O H H H H OCH3
C C H C C H C C H
H C C CH3O C C H C C
H H H H H H
1 2 3
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711
1
H NMR Spectra of Methoxibutadienes - Methoxy Signals not Shown here.
6.4 6.0 5.6 5.2 4.8 4.4 4.0
6.4 6.0 5.6 5.2 4.8 4.4 4.0
6.4 6.0 5.6 5.2 4.8 4.4 4.0

(ppm)
1
Figure 527 : Simulated 500 MHz H NMR spectra of methoxybutadienes. Upper: 1. Middle: 2. Lower: 3.
H146197_00_01
712
1
H NMR Data of Methoxybutadienes 1 to 3
Parameter Type Data 1 Data 2 Data 3
δ1 3.50 5.70 4.0690 [ppm]
δ2 6.53 3.52 4.0423 [ppm]
δ3 5.43 4.97 3.5923 [ppm]
δ4 6.14 6.60 6.0423 [ppm]
δ5 4.88 4.92 5.4823 [ppm]
δ6 4.72 4.77 5.0240 [ppm]

2
J12 JHH (gem) - - 1.90 [Hz]
3
J13 JHH (cis) - 6.18 - [Hz]
4
J14 JHH (t) - 0.96 0 [Hz]
5
J15 JHH (tc) - 0.75 0.51 [Hz]
5
J16 JHH (tt) - 1.55 1.50 [Hz]
3
J23 JHH (trans) 12.5 - - [Hz]
4
J24 JHH (c) 0.5 - 0 [Hz]
5
J25 JHH (cc) 0.6 - 0.51 [Hz]
5
J26 JHH (tc) 0.6 - 0.57 [Hz]
3
J34 JHH (s) 10.5 10.8 - [Hz]
4
J35 JHH (c) 0.5 0.8 - [Hz]
4
J36 JHH (t) 0.6 0.81 - [Hz]
3
J45 JHH (trans) 16.8 17.2 17.27 [Hz]
3
J46 JHH (cis) 10.3 10.4 10.82 [Hz]
2
J56 JHH (gem) 2.0 2.18 1.87 [Hz]
Blue: Butadiene protons, ABCDE. Magenta: Methoxy groups, X3 singlet.
Data from:
a) J. P. Dorie, M. L. Martin, S. Odiot and F. Tonnard; Org. Magn. Res. 5, 265-270 (1973)
b) R. T. Hobgood, Jr. and H. G. Goldstein; J. Mol. Spec. 12, 76-86 (1964)
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17.2 ABCDE and ABCDEX Spin Systems in 2-Fluorobutadiene
For 2-fluorobutadiene an ABCDEX is found at lower fields. For higher fields full first order systems
are calculated. Study the NMR spectra of this interesting compound.
H F
C C H
H C C
H H
NMR Data of 2-Fluorobutadiene - ABCDEX Spin system
Parameter Type Data
δ1 δH 4.593 [ppm]
δ2 δH 4.319 [ppm]
δ3 δH 6.061 [ppm]
δ4 δH 5.518 [ppm]
δ5 δH 5.116 [ppm]
δ6 δF -114.4 [ppm]
2
J12 JHH (gem) -2.74 [Hz]
3
J13 JFH (cis) 15.76 [Hz]
4
J14 JHH (t) 0.095 [Hz]
5
J15 JHH (tc) 0.62 [Hz]
5
J16 JHH (tt) 1.49 [Hz]
3
J23 JFH (trans) 47.93 [Hz]
4
J24 JHH (c) -0.19 [Hz]
5
J25 JHH (cc) 0.70 [Hz]
5
J26 JHH (tc) 0.73 [Hz]
3
J34 JFH (s) 25.15 [Hz]
4
J35 JFH (c) 0.41 [Hz]
4
J36 JFH (t) 1.19 [Hz]
3
J45 JHH (trans) 17.32 [Hz]
3
J46 JHH (cis) 11.145 [Hz]
2
J56 JHH (gem) 1.24 [Hz]
Data from: A. A. Bothner-By and R. K. Harris; J. Amer. Chem. Soc. 87, 3445-3450 (1965).
1
This paper reports also H NMR spectra and data for chloroprene CH2=CCl-CH=CH2.
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714
1 1 19
Simulated H and H{ F} NMR Spectra of 2-Fluorobutadiene - Total
6.0 5.6 5.2 4.8 4.4
6.0 5.6 5.2 4.8 4.4

(ppm)
1 19 1
Figure 528 : Simulated NMR spectra of 2-fluorobutadiene. Upper: 500 MHz H{ F}. Lower: H.
1
Simulated 500 MHz H NMR Spectrum of 2-Fluorobutadiene - Expanded
3060 3050 3040 3030 3020 3010 3000
3060 3050 3040 3030 3020 3010 3000

(Hz)
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1
Simulated 500 MHz H NMR Spectrum of 2-Fluorobutadiene - Expanded
H146197_00_01
716
19
Simulated F NMR Spectra of 2-Fluorobutadiene
-53620 -53640 -53660 -53680 -53700 -53720

(Hz)
19
Figure 529 : 470 MHz F NMR Spectra of 2-Fluorobutadiene. X Part.
Exercise: Assign the protons and the fluorine atom to data listed above. Simulate and analyze
spectra. Use DAISY and Multiplet analysis tools in TopSpin.
17.3 The [ABC]2 - [AMX]2 in Perfluorobutadiene

CF2=CF-CF=CF2
19
Mannat and Bowers analyzed the F NMR spectrum of perfluorobutadiene.
A C F F 1 3
B´ C C F 5
B F C C 2
C´ A´ F F 4 6
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717
Results from spectral analysis are listed below.
19
F NMR Data from CF2=CF-CF=CF2

δi
1=6 A = A´ δF -93.8586 [ppm]
2=5 B = B´ δF -107.9558 [ppm]
3=4 C = C´ δF +179.6853 [ppm]
νi
1=6 A = A´ νF -5297.9613 [Hz]
2=5 B = B´ νF -6093.6947 [Hz]
3=4 C = C´ νF +10142.5524 [Hz]
Jik
2
12 = 56 JAB JFF 50.737 [Hz]
3
13 = 46 JAC JFF (cis) 31.911 [Hz]
4
14 = 36 JAC´ JFF (t) 2.409 [Hz]
5
15 = 26 JAB´ JFF (tc) 2.449 [Hz]
5
16 JAA´ JFF (tt) 4.800 [Hz]
3
23 = 45 JBC JFF (trans) -118.577 [Hz]
4
24 = 35 JBC´ JFF (c) 14.195 [Hz]
5
25 JBB´ JFF (cc) 11.313 [Hz]
3
34 JCC´ JFF -30.305 [Hz]
HWB 0.300 [Hz]
Data from: S. L. Mannatt, M. T. Bowers; J. Amer. Chem. Soc. 91, 4381-4394 (1969).
19
Simulated 56 MHz F NMR spectra are shown in subsequent figures:
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19
Simulated 56 MHz F NMR Spectrum
-5160 -5220 -5280 -5340 -5400

(Hz)
-6000 -6060 -6120 -6180 -6240

(Hz)
10260 10200 10140 10080 10020

(Hz)
19
Figure 530 : Simulated 56 MHz F NMR spectrum. Upper: A part. Middle: B part. Lower: C part.
H146197_00_01
719
1 19
While the H NMR spectrum of butadiene CH2=CH-CH=CH2 is rather complex, the F NMR
spectrum of perfluorobutadiene corresponds to an [ABC]2 system approximating the [AMX]2
situation even at low fields. Explicit algebraic equations for transition frequencies and intensities
19
were derived by Mannat and Bowers. 206 lines were calculated by DAISY for the total 56 MHz F
NMR spectrum. Three regions are observed, holding spectral parts symmetrically arranged around
corresponding resonance frequencies. Each part exhibits 4 strong lines, so called N-lines. For a
start concentrate on those N-lines, which form the lines of a parent AMX type system. Analysis of
this system directly yields resonance frequencies νA, νM, νX and splittings corresponding to
NAM = JAM + JAM´ NAX = JAX + JAX´ NMX = JMX + JMX´.
In order to obtain the missing parameters
LAM = JAM - JAM´ LAX = JAX - JAX´ LMX = JMX - JMX´
JAA´ JMM´ JXX´
follow the algebraic route listed in the paper of Mannat and Bowers or use automated analysis by
TopSpin / DAISY.
Starting values for iterations are given in this paper of Mannat and Bowers, where NMR data from
several substituted fluorobutadienes are discussed. Of particular interest is 1,1,4,4-
tetrafluorobutadiene CF2=CH-CH=CF2 which exhibits an interesting [ABX]2 spectrum. Proton
19 1
decoupling F{ H} delivers the typical features of an [AB]2 spectrum.
For details read:

K. L. Servis, J. D. Roberts; J. Amer. Chem. Soc. 87, 1339-1344 (1965).
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Auxiliary Graphics: Comparing [AMX]2 with AMX
400 200 0 -200 -400

(Hz)
Hypothetical [AMX]2 with all Jik set to corresponding JFF from CF2=CF-CF=CF2.
Hypothetical AMX with JAM, JAX, JMX set to NAM, NAX, NMX from CF2=CF-CF=CF2.
H146197_00_01
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Five to Seven Spins: Cycloalkanes
18 Five to Seven Spins:

Cycloalkanes
18.1 Five to Seven Spins – Cyclopropanes
Monosubstituted Cyclopropanes - [AB]2C

H H 4 3
R R
H H 5 2
H 1
1
In the early days of NMR unusually low H chemical shifts were observed in [AB]2C type systems of
cyclopropyl compounds, e.g.:
1
H NMR Data of c-C3H5R (R = Br, COOH, Li)
R = Br R = COOH R = Li
in CCl4 in CCl4a in THF
a) a) b,c,d)
δi Type Data Data Data

1 C δH 2.84 1.58 (-) 2.50 [ppm]
2,5 B, B´ δH 1.00 0.97 (+) 0.46 [ppm]
3,4 A, A´ δH 0.88 1.06 (-) 0.05 [ppm]
Jik
3
12, 15 BC, BĆ JHH(cis) 7.3 8.0 11.8 [Hz]
3
13, 14 AC, AĆ JHH(trans) 3.9 4.6 9.5 [Hz]
2
23, 45 AB, A´B´ JHH(gem) -5,9 -4.3 -0.5 [Hz]
3
24, 35 AB´, A´B JHH(trans) 6.6 7.5 1.5 [Hz]
3
25 BB´ JHH(cis) 10.3 10.5 ? [Hz]
3
34 AA´ JHH(cis) 10.0 11.0 3.0 [Hz]
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Data from e.g.:

a) K. B. Wiberg, B. J. Nist; J. Amer. Chem. Soc. 85, 2788-2790 (1963).
b) T. Schaefer, F. Hruska, G. Kotowycz; Can. J. Chem. 43, 75-80 (1965). Compare ref.
c) D. Seyferth, H. M. Cohen; J. Org. Met. Chem. 1, 15-21 (1963).
d) signs of shifts adjusted to general definitions.
Diamagnetic upfield shifts were explained by aromatic ring currents effects as described in:
a) "Chemical implications of σ-conjugation". M. J. S. Dewar; J. Amer. Chem. Soc. 106, 669 - 682
(1984).
b) "Ring Current Model and Anisotropic Magnetic Response of Cyclopropane". R. Carion, B.
Champagne, G. Monaco, R. Zanasi, S. Pelloni, P. Lazzeretti; J. Chem. Theory Comput. 6,
2002 - 2019 (2010).
The parent compound cyclopropane is characterized by an A6 singlet signal resonating as low as
δH = 0.22 ppm. (K. B. Wiberg, B. J. Nest; J. Amer. Chem. Soc. 83, 1226-1230 (1961)).
Note: Increasing electronegativity of substituents R in c-C3H5R decreases the coupling constants

2 3 3
JHH (H2,H4), JHH(cis) (H1,H2), and JHH(trans) (H1,H3).
1
We need those observations to understand and interrogate the following reports on H NMR
studies on propyleneoxide derivatives and related compounds - ABCD3, ABCDE, ABCDEX,
[ABC]2.
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724
18.1.1 Propyleneoxide – ABCD3
H CH3 1 4
H O H 2 O 3
1
H NMR Data of Propylene Oxide
δi Type Data
1 C δH 2.279 [ppm]
2 B δH 2.589 [ppm]
3 A δH 2.849 [ppm]
4 D3 δH 1.214 [ppm]
Jik
2
12 BC JHH +5.37 [Hz]
3
13 AC JHH(trans) +2.57 [Hz]
4
14 CD JHH(cis) -0.36 [Hz]
3
23 AB JHH(cis) +3.88 [Hz]
4
24 BD JHH(trans) +0.5 [Hz]
3
34 AD JHH +5.15 [Hz]
Data from: D. D. Elleman, S. L. Manatt, C. D. Pearce; J. Chem. Phys. 42, 650 (1965).
1 1
This paper introduces the ABCD3 theory and H{ H} DR determination of signs from coupling
constants.
2
Note: The geminal coupling JHH = J23 is given above with positive sign.
1
Exercise: Remeasure, analyze and iterate the H NMR spectrum of propyleneoxide on your local
spectrometer. Compare your data with results from Ellemann et al..
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18.1.2 Epichlorhydrine and Related Structures – ABCDE
H
H R
H
H O H R = Cl, Br, OOCH3
1
H NMR Data of Epichlorhydrine (in CDCl3)
δi Type Data
1 E δH 2.697 [ppm]
2 D δH 2.905 [ppm]
3 C δH 3.252 [ppm]
4 B δH 3.583 [ppm]
5 A δH 3.578 [ppm]
Jik
2
12 DE JHH 4.81 [Hz]
3
13 CE JHH(trans) 2.49 [Hz]
4
14 BE JHH(cis) -0.36 [ppm]
4
15 AE JHH(cis) -0.28 [ppm]
4
23 CD JHH(trans) 3.91 [Hz]
4
24 BD JHH(trans) 0.35 [Hz]
4
25 AD JHH(trans) 0.27 [Hz]
3
34 BC JHH 5.73 [Hz]
3
35 AC JHH 5.00 [Hz]
2
45 AB JHH -11.50 [Hz]
Data from: R. J. Abraham, B. R. Richards; Tetrahedron 39, 4201-4208 (2983)
2
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18.1.3 Epifluorhydrine – ABCDEX
H 4
H F 1 6
H 5
H O H 2 O 3
Epifluorhydrine in CDCl3.
δi Type Data
1 E δH 2.663 [ppm]
2 D δH 2.854 [ppm]
3 C δH 3.249 [ppm]
4 B δH 4.288 [ppm]
5 A δH 4.651 [ppm]
6 X δF - [ppm]
Jik
2
12 DE JHH 4.90 [Hz]
3
4
14 BE JHH(cis) -0.20 [ppm]
4
15 AE JHH(cis) -0.31 [ppm]
4
16 AX JFH(cis) -1.22 [ppm]
4
4
24 BD JHH(trans) 0.1 [Hz]
4
25 AD JHH(trans) 0.0 [Hz]
4
26 DX JFH(trans) 3.67 [Hz]
3
34 BC JHH 5.88 [Hz]
3
35 AC JHH 2.56 [Hz]
3
36 CX JFH 12.25 [Hz]
2
45 AB JHH -10.25 [Hz]
2
46 BX JFH 47.17 [Hz]
2
56 AX JFH 47.61 [Hz]
Data from: R. J. Abraham, B. R. Richards; Tetrahedron 39, 4201-4208 (2983)

2
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18.1.4 Dioxidobutane – [ABC]2
H O H 4 O 5
H 1
H 6
H O H 2 O 3
1
H NMR Data of Dioxidobutane (5 % v/v in CDCl3)
δi Type Data
1=6 δH [ppm]
2=5 δH [ppm]
3=4 δH [ppm]
νi Type Data
1=6 A, A´ δH 768.023 [Hz]
2=5 B,B´ δH 740.350 [Hz]
3=4 C, C´ δH 783.169 [Hz]
Jik
2
12 = 56 AB JHH 5.182 [Hz]
3
13 = 46 AC JHH(trans) 4.214 [Hz]
4
14 = 36 AC´ JHH(cis) -0.068 [Hz]
5
15 = 26 AB´ JHH(cis,trans) 0.057 [Hz]
5
16 AA´ JHH(cis,cis) 0.262 [Hz]
3
23 = 45 BC JHH(cis) 2.625 [Hz]
4
24 = 35 BC´ JHH(trans,cis) -0.141 [Hz]
5
25 BB´ JHH(trans,trans) 0.015 [Hz]
3
34 CC´ JHH 5.255 [Hz]
Data from: G. Gatti, A. Demarco; Org. Magn. Res. 5, 53-56 (1973).
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2
2
It seems strange, that signs of geminal coupling constants JHH from the cyclopropyl and the CH2R
units should be different for cases shown above.
2
And indeed H. Günther and D. Wendisch showed, that the sign of JHH (H1,H2) from the
cyclopropylring in
H H 5 6
H 3
H 7
H 2
R H 4
H 1 R = NCO
is negative! Read this interesting paper on the ABCDEFG spectrum of trans-vinyl-cyclo-

propylisocyanate. Analogous results for trans- and cis-vinyl-cyclo-propanecarboxylic acid
methylesters (R = COOCH3) are given as well.
H H 5 6
H 3
H 7
H 2
CH3OOC H 4
H 1
H H 5 6
CH3OOC
H 7
H 2
H H 3 4
H 1
Simulate those ABCDEFG spectra which approximate a first order case at higher fields, e. g. when
1
using 500 MHz H NMR.
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1
A final proof was achieved by iteration of a good 200 MHz H NMR spectrum of glycidyl-acetate
provided by C. Rabiller, Nantes.
H
H OOCCH3
H
H O H
2
Both coupling constants JHH in this molecule have negative signs!
1
H NMR Data of Glycidylacetate (in CDCl3)
δi Type Data
1 E δH 3.3177 [ppm]
2 D δH 3.5695 [ppm]
3 C δH 4.0215 [ppm]
4 B δH 4.8875 [ppm]
5 A δH 5.8204 [ppm]
Jik
2
12 DE JHH -4.826 [Hz]
3
3
3
34 BC JHH 6.410 [Hz]
3
35 AC JHH 3.028 [Hz]
2
45 AB JHH -12.289 [Hz]
4
Remark: JHH (J14, J15, J24, J25) are negligibly small, set to zero, not iterated.
Data from: C. Rabiller; S. Goudetsidis, G. Hägele; Heinrich-Heine-University, Düsseldorf,

unpublished.
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18.2 Cyclobutanes: ABCDE at Lower Fields, AHKRX at Higher

Fields
19
18.2.1 F NMR Spectrum of 1,1,2-Trichloro-2,3,3,4,4-pentafluoro-
cyclobutane
Co-cyclodimerisation of CF2=CCl2 and CF2=CClF yielded the mixture of C4Cl8-iFi (i = 4-6) isomers:
19
C4Cl4F4 gives rise to an A4 system, a sharp singlet in F NMR, which may be used as a reference
with δF = 114.2 ppm vs. CFCl3. Both cis- and trans-C4Cl2F6 isomers yield [ABC]2 cases. Obviously
head-to-head / tail-to-tail dimers are formed. This is true for C4Cl3F5 as well. 1,1,3-trichloro-
2,2,3,4,4-pentafluorocycobutane potentially showing an [AB]2C system, is not formed, only 1,1,2-
trichloro-2,3,3,4,4-pentafluorocycobutane is observed and recognized by its ABCDE to AHKRX
system, which will be studied below.
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NMR Parameters for 1,1,2-Trichloro-2,3,3,4,4-pentafluoro-cyclo-butane

δi
1 A 47.245 [ppm]
2 B 45.450 [ppm]
3 C 43.607 [ppm]
4 D 41.383 [ppm]
5 E 37.214 [ppm]
νi
1 A 22223.34 [Hz]
2 B 21378.10 [Hz]
3 C 20512.08 [Hz]
4 D 19466.88 [Hz]
5 E 17504.91 [Hz]
1 A 22223.34 [Hz]
Jik
3
12 AB JFF cis -10.47 [Hz]
2
13 AC JFF 200.98 [Hz]
4
14 AD JFF trans 7.86 [Hz]
3
15 AE JFF trans 4.58 [Hz]
3
23 BC JFF trans 3.99 [Hz]
3
24 BD JFF trans -2.14 [Hz]
2
25 BE JFF 213.33 [Hz]
4
34 CD JFF cis -2.14 [Hz]
3
35 CE JFF cis -7.71 [Hz]
3
45 DE JFF cis -8.08 [Hz]
HWB
global 0.30 [Hz]
50% in CCl4. Chemical shifts referenced vs. C6F6. ABCDE system at lower and AHKRX at higher
fields.
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19
Simulated as 470 MHz F NMR spectrum below.
47 46 45 44 43 42 41 40 39 38 37
(ppm)
Figure 531 : Total spectrum. Geminal pairs are indicated: AC and BE.
47.50 47.40 47.30 47.20 47.10 47.00

(ppm)
Figure 532 : Part A - analyze as dddd
45.70 45.60 45.50 45.40 45.30 45.20

(ppm)
Figure 533 : Part B - analyze as dddd
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733
43.80 43.70 43.60 43.50 43.40

(ppm)
Figure 534 : Part C - analyze as dddd
41.50 41.40 41.30

(ppm)
Figure 535 : Part D - analyze as dddd to deceptively simple tt
37.40 37.30 37.20 37.10 37.00

(ppm)
Figure 536 : Part E - analyze as dddd
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Read:
a) G. Bauer, G, Hägele, P. Sartori; Z. Naturforsch. 34b, 1249-1251 (1979).
b) G. Bauer; PhD Thesis 1977, Heinrich Heine Universität Düsseldorf.
18.2.2 The 6-Spin [AMX]2 Case of Cis-1,2-Dichlorohexafluorocyclobutane
19
The [AMX]2 pattern from the F NMR spectrum of cis-1,2-dichlorohexafluorocyclobutane
was studied by V. J. Gazzard and R. K. Harris (Org. Magn. Res. 6, 404-406 (1974)).
The underlaying theory of [AMX]2 system was developed by E. Lustig, N. Duy, P. Diehl, H.
Kellerhals; (J. Chem. Phys. 48, 5001-5007 (1968)) with experimental spectra from 1,2,3,4-
tetrafluorobenzene. Suggestion: Read those publications.
18.2.3 ABCDEX – AHKRTX in 1,2-Dibromo-2,3,3,4,4-pentafluorocyclobutane
2,3,3,4,4-Pentafluorocyclobutene reacts with bromine to yield the mixture of cis and trans isomers
1
of 1,2-dibromo-2,3,3,4,4-pentafluorocyclobutane. Isomers are identified stereospecifically by H
19
and F NMR spectra. While trans-1,2-dibromo-2,3,3,4,4-pentafluorocyclobutane gives rise to a
straight ABCDEX to AHKRTX system, easy to analyze, the cis isomer is less convenient showing
an overlap of C- and E- (or K- and T-) fluorine signals. Here it suffices to study the trans isomer:
F F Br F F
F
F +Br2 F Br F Br
+
F F F F Br
F H F H F H
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NMR Data of Trans-1,2-dibromo-2,3,3,4,4-pentafluorocyclobutane

F F D E
F Br C
F Br B
F H A X
Parameter Type Data

δi [ppm]
A δF 52.00
B δF 47.57
C δF 42.39
D δF 37.49
E δF 32.93
X δH 4.743
Jik [Hz]
3
AB JFF cis -10.31
2
AC JFF +210.43
3
AD JFF trans +5.12
4
AE JFF trans +8.70
3
AX JFH cis +9.94
3
BC JFF trans +4.60
2
BD JFF +209.54
3
BE JFF trans -6.17
4
BX JFH cis +7.61
3
CD JFF cis -7.25
4
CE JFF cis -0.14
3
CX JFHtrans +9.15
3
DE JFF cis -8.39
4
DX JFH trans -2.23
3
EX JFHtrans +10.99
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736
54 52 50 48 46 44 42 40 38 36 34 32
(ppm)
19
Figure 537 : Total 470 MHz F NMR spectrum. Geminal pairs indicated by AC and BD.
52.30 52.20 52.10 52.00 51.90 51.80 51.70

(ppm)
Figure 538 : A part - analyze as ddddd
47.90 47.80 47.70 47.60 47.50 47.40 47.30

(ppm)
Figure 539 : B part - analyze as ddddd
42.70 42.60 42.50 42.40 42.30 42.20 42.10

(ppm)
Figure 540 : C part - analyze as ddddd
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37.70 37.60 37.50 37.40 37.30 37.20

(ppm)
Figure 541 : D part - analyze as ddddd
33.00 32.90 3
(ppm)
Figure 542 : E part - analyze as ddddd approximately as dtt
4.78 4.76 4.74 4.72 4.70

(ppm)
Figure 543 : X part - analyze as ddddd
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738
NMR Data of Cis-1,2-dibromo-2,3,3,4,4-pentafluorocyclobutane

F Br A
F Br C
F F D E
F H B X
Parameter Type Data

δi [ppm]
A δF 51.81
B δF 47.58
C δF 43.59
D δF 32.40
E δF 43.75
X δH 4.832
Jik [Hz]
3
AB JFF trans +5.34
3
AC JFF cis -11.39
2
AD JFF +206.42
3
AE JFF trans -0.97
4
AX JFH trans -1.79
2
BC JFF +212.49
3
BD JFFcis -7.00
4
BE JFF cis -5.77
3
BX JFH cis +11.64
3
CD JFF trans +4.31
4
CE JFF trans +13.36
3
CX JFHcis +10.05
3
DE JFF cis -6.32
4
DX JFH cis +8.30
3
EX JFH cis +16.70
Exercise: Simulate spectra of the cis isomer and compare with the spectra of the trans isomer.
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Remarks: Spectra from fluorinated cyclobutanes shown above were not too difficult to understand
and analyze. But normal hydrogen containing cyclobutanes give rise to intricate, complex spectra
even at elevated fields. A single example will suffice to demonstrate this situation.
18.2.4 Seven Spins – A[BC]2DE from Cyanocyclobutane – Even at 800 MHz
H H 3c 2c D B 4 2
H CN 4c B´ 6
H H 3t 2t E C 5 3
H H 4t 1 C´ A 7 1
1
The 800 MHz H NMR spectrum of cyanocyclobutane (c-butyl nitril) appears in three spectral
ranges:
Spins Hydrogens Range [Hz]

A H1 2500-2464
B, B´ and C, C´ H2c, H4c and H2t, H4t 1946-1873
D and E H3t and H3c 1689-1631
1
Figure 544 : Total 800 MHz H NMR spectrum cyanocyclobutane in CDCl3
1
corresponding to the 7 spins A, BBĆC´, D and E of A[BC]2DE. This H NMR spectrum is complex
even when measured at very high field, at 800 MHz. 522 lines with intensities > 0.001 are
calculated when using DAISY. The A part appears as a deceptively simple doublet of quintets, but
the remaining spectral parts are beyond manual analysis.
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Expansions of those ranges are shown below in 3 separate plots:
2505 2490 2475 2460 2445

(Hz)
Figure 545 : A part
1935 1920 1905 1890 1875

(Hz)
Figure 546 : BBĆC´ part
1695 1680 1665 1650 1635

(Hz)
Figure 547 : D,E part
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Spin Enumeration and NMR Data Used for DAISY
δi Type [ppm]
1 1 δH 3.102
2 2c δH 2.405
3 2t δH 2.375
4 3c δH 2.069
5 3t δH 2.079
6 4c δH 2.405
7 4t δH 2.375
νi [Hz]
1 1 νH 2481.6
2 2c νH 1923.2
3 2t νH 1900.0
4 3c νH 1655.2
5 3t νH 1663.2
6 4c νH 1923.2
7 4t νH 1900.0
n
Jik n Type [Hz]
12 1,2c 3 trans 8.36
13 1,2t 3 cis 8.55
14 1,3c 4 trans -1.12
15 1,3t 4 cis 0.30
16 1,4c 3 trans 8.36
17 1,4t 3 cis 8.55
23 2c,2t 2 gem -11.59
24 2c,3c 3 cis 9.23
25 2c,3t 3 trans 8.87
26 2c,4c 4 cis 0.70
27 2c,4t 4 trans -0.83
34 2t,3c 3 trans 4.23
35 2t,3t 3 cis 8.82
36 2t,4c 4 trans -0.83
37 2t,4t 4 cis 3.33
45 3c,3t 2 gem -11.58
46 3c,4c 3 cis 9.23
47 3c,4t 3 trans 4.23
56 3t,4c 3 trans 8.87
57 3t,4t 3 cis 8.82
67 4c,4t 2 gem -11.59
HWB global 0.5
Ca. 10 mg cyanocyclobutane in CDCl3 and TMS as int. ref. in 5 mm sample.
Data: R. J. Abraham, P. Leonard, C. F. Tormena; Magn. Reson. Chem. 49, 23-29 (2011).
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Please bear in mind the signs of proton-proton coupling constants in cyclobutanes:
2
sign( JHH) negative
3
sign(cis JHH) positive
3
sign(trans JHH) positive
4
sign(cis JHH) positive
4
sign(trans JHH) negative
In addition to cyanocyclobutane Abraham, Leonard, and Tormena report on a series of cyclobutyl

compounds like c-C4H7R (R = H, OH, NH2, Cl, Br, I, COOMe, COPh, COOEt, CH2Br, CH2OH).
NMR parameters, conformations, and chemical shift calculations are discussed in this interesting
paper quoted above.
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Four to Eight-Spins: Cycloalkenes
19 Four to Eight Spins: Cycloalkenes
Cyclobutene and fluorocyclobutenes give rise to interesting NMR spectra and several basic
papers were published developing the theory of corresponding spin systems. A few examples are
listed in abbreviated form:
H H H H F F
H H H H F F F F F F F F
[A[B]2]2 [A[X]2]2 [X[Y]2]2

a b, d b, c, d
F H F Cl H Cl Br Cl Cl Cl
F F F F F F F F F F F F F F F F F F F F
AX[YZ]2 X[YZ]2 A[XY]2 [XY]2 [[X]2]2

d b, d d d d
Cl F
F F
F F
F F
F F
F F
F F F F F F F F
A[BCDE]2 [A[BC]2]2
f g
Details of the spectral properties will not be discussed in this manuscript. If you need to get a
deeper understanding of such systems read:
a) H. Hüther, H. A. Brune; Org. Magn. Res. 3, 737-757 (1971)
b) R. K. Harris, V. J. Robinson; J. Magn. Res. 1, 362-377 (1969)
c) R. K. Harris, R. Ditchfield; Spectrochimica Acta 24A, 2089-2105 (1968)
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Four to Eight Spins: Cycloalkenes
d) G. Bauer; PhD Thesis, Universität Düsseldorf, 1977.

e) G. Bauer, G. Hägele; Z. f. Naturforsch. 34b, 1252-1259 (1979)
f) R. A: Newmark, G. R. Apai, H. E. Romine; J. Magn. Res. 1, 562-567 (1969).
g) G. Hägele, M. Engelhardt, W. Boenigk; "Simulation und automatisierte Analyse von
Kernresonanzspektren". VCH, Weinheim, 1987, p. 92.
Here we wish to direct your interest only towards one particular example.
19.1 [A6[M]2X]2 – 1,1,2,2-Tetrafluoro-cyclobutene-3,4-bis-

phosphonic Acid Tetramethylester
(H3CO)2(O)P P(O)(OCH3)2 1 2 7 8
F F F F 3 4 6 5
[A6[M]2X]2
d,e
It was investigated by single and double resonance techniques:
Spectral Techniques Systems

1 19 31
H F P [A6[M]2X]2
1 19 31 19
H{ F} P{ F} [A6X]2
19 1 31 1
F{ H} P{ H} [[M]2X]2
1 31 19 31
H{ P} F{ P} A6 + [[M]2]2
Experimental chemical shifts for this complex [A6[M]2X]2 case were found: δH = 3.826 ppm.
δF = 51.953. δP = 0.800 ppm.
In order to simplify calculations (and intuitive understanding), resonance frequencies were set to νH
= 200 Hz. νF = 0 Hz. νP = -200 Hz as shown below.

3 6 3 4
Observe the strong N-lines: NAX = JAX+JAX´ = JPH + JPH. NMX = JMX+JMX´ = JPF + JPF.
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Simulated Spectra
2.8 2.6 2.4 2.2 2.0 1.8 1.6 1.4 1.2

(ppm)
Figure 548 : Simulated H NMR spectrum where νH is defined to 200 Hz. A part.
1
80 40 0 -40 -80
(Hz)
F NMR spectrum where νF is set to 0 Hz. M part.

19
Figure 549 : Simulated
-120 -160 -200 -240 -280

(Hz)
P NMR spectrum where νp is set to -200 Hz. X part.

31
Figure 550 : Simulated
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747
NMR Parameters Used for Simulation
Parameter Type Type

νi [Hz]
1=8 νA νH 200*
2=7 νX νP -200*
3=4=5=6 νM νF 0*
Jik [Hz]
3
12 = 78 JAX JPH 11.52
6
13 = 14 = 57 = 58 JAM JFH 0
7
15 = 16 = 38 = 48 JAM´ JFH 0
6
17 = 28 JPH JPH 0
9
18 JAX´ JHH 0
3
23 = 24 = 57 = 67 JMX JPF -4.63
4
25 = 26 = 37 = 47 JMX´ JPF 14.23
3
27 JXX´ JPP 4.73
2
34 = 56 JMM´ JFF 201.39
3
35 = 46 JMM´´ JFF -12.57
3
36 = 45 JMM´´´ JFF 31.16
HWB 0.3
*)
simplified resonance frequencies, see comments above
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19.2 Fluorocyclopentenes
R R R´ R F R
F F F F F F
F F F F F F
F F F F F F
R = Cl, I R = Cl; R´ = I R=I
[[A]2X]2 [AMX]2 [AMX]2B
Read the fundamental paper of: L. Cavalli, R. K. Harris; J. Magn. Res. 10, 355-371 (1973).
An automated analysis of the [A[B]2C]2 spectrum from perfluorocyclopentene
F F
F F
F F
F F
was described by: G. Hägele, M. Engelhardt, W. Boenigk; "Simulation und automatisierte Analyse
von Kernresonanzspektren". VCH, Weinheim, 1987, p. 100.
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Five to Six Spins: Phenyl and Pentafluorophenyl Groups
20 Five to Six Spins: Phenyl and

Pentafluorophenyl Groups
20.1 Five to Six Spins – Phenyl Groups in C6H5R
1
H NMR Spectra of Phenyl Groups C6H5R
Compounds C6H5R bearing phenyl groups attached to achiral substituents R
R R
H H 5 1
H H 4 2
H 3
when dissolved in achiral solvents give rise to spin systems characterized by a two-fold symmetry.
Each pair of ortho-protons (H1,H5) and meta-protons (H2,H4), is chemically equivalent.
Substituent effects due to R influence strongly the chemical shifts δ1 = δ5, δ2 = δ4 and δ3, less
3 3 4
strongly coupling constants J12 = J45, J15 and to a lesser degree the remaining coupling constants
4 4 5 5 3 3 4
J13 = J35, J14 = J25, J23 = J34, and J24.
Hence six possible spin systems might be expected:
R R R
A´ A B´ B C´ C
B´ B A´ A A´ A
C C B
[AB]2C [BA]2C [CA]2B
R R R
A´ A B´ B C´ C
C´ C C´ C B´ B
B A A
[AC]2B [BC]2A [CB]2A
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751
Practical examples are found for [AB]2C, [AC]2B, [BA]2C, [CA]2B but not for [BC]2A and [CB]2A as
shown in the following table:
Spin system Substituent R in Compounds C6H5R

+
[AB]2C C6H5, CCl3, N(CH3)4 , P(C6H5)2, SC6H5, Cl , CH3, CH=CH2
CN, CHO, COCH3, COCl, COOCH3, COCH2CH3, COOCH(CH3)2, NO, NO2,
[AC]2B
SO3CH3, SO2Cl, Br, I
[BA]2C OC6H5
[BC]2A - not found
[CA]2B NH2, NHCH3, N(CH3)2, OH, OCH3, OCH2CH=CH2, OCOCH3, F
[CB]2A - not found
Most common are spectral types [AC]2B and [CA]2B. Throughout the following pages spin systems
will be assigned according to [HorthoHmeta]2Hpara.
1
Typical patterns from simulated 500 MHz H NMR spectra of C6H5R are shown below using data
from S. Castellano, C. Sun, R. Kostelnik; Tetr. Lett. 51, 5205-5209 (1967).
[AB]2C [AC]2B [AC]2B [CA]2B

+ -
Parameter [C6H5N(CH3)3] I C6H5NO C6H5NO2 C6H5NH2
ν1 = ν 5 3989.550 3906.642 4095.392 3228.550
ν2 = ν 4 3829.200 3773.742 3760.017 3504.150
ν3 3801.950 3805.225 3826.483 3309.300

3 3
J12 = J45 8.554 7.907 8.361 8.018
4 3
J13 = J35 0.930 1.276 1.176 1.105
5 5
J14 = J25 0.451 0.555 0.550 0.468
4
J15 3.120 1.974 2.396 2.530
3 3
J23 = J34 7.470 7.414 7.468 7.389
4
J24 1.660 1.362 1.484 1.595
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Simulated Spectra
8.00 7.90 7.80 7.70 7.60

(ppm)
+ -
Figure 551 : N,N,N-Trimethlyaniliniumiodide [C6H5N(CH3)3] I . [AB]2C.
7.80 7.75 7.70 7.65 7.60 7.55

(ppm)
Figure 552 : Nitrosobenzene C6H5NO. [AC]2B.
8.20 8.10 8.00 7.90 7.80 7.70 7.60 7.50

(ppm)
Figure 553 : Nitrobenzene C6H5NO2. [AC]2B.
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7.05 6.90 6.75 6.60 6.45

(ppm)
Figure 554 : Aniline C6H5NH2. [CA]2B.
Some Comments to Manual or Automated Analysis of 1H NMR Spectra from C6H5R
1
Do we really need to perform a detailed manual analysis for H NMR spectra of C6H5 groups? The
answer clearly is: NO! It suffices to use the tools for automated analysis and iteration implemented
in TopSpin / DAISY. To get starting values for iterations inspect the spectral part of the para-proton
H3 and obtain good approximations for coupling constants J13 and J23 and the chemical shift δ3.
Than inspect the two remaining spectral parts and identify repeated spacings due to J13 and J23.
Since J13 < J23 ortho-protons (H1,H5) and meta-protons (H2,H4) are identified leading to starting
values for the corresponding chemical shifts δ1 = δ5 and δ2 = δ4. Start iterations with the remaining
estimated parameters:
3 3
Ortho couplings J12 = 7.8-8.6 Hz J23 = 7.3-7.6 Hz
4 4 4
Meta couplings J15 = 1.8-2.7 Hz J24 = 1.3-1.8 Hz J13 = 0.9-1.3 Hz
5
Para couplings J14 = 0.3-0.6 Hz
and remember two rules:

3
ortho couplings JHH J12 > J23
4
meta couplings JHH J15 > J24 > J13
This will do and convergence of iteration should be achieved rapidly. Study in detail one example,
e. g.: bromobenzene C6H5Br. Bear in mind that chemical shifts δH from ortho-, meta- and para-
protons in C6H5R are individually sensitive to substituent and solvent effects. Meticulous studies
should use shifts at “infinite dilution” by extrapolating results from concentration series.
Read details: K. Hayamizu, O. Yamamoto; J. Mol. Spec. 28, 89-100 (1968).
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1
[AC]2C System in 500 MHz H NMR Spectrum of C6H5Br
Parameter Parameter Type Data [Hz]

ν1 = ν5 νA = νA´ νH (ortho) 3647.05
ν2 = ν4 νC = νC´ νH (meta) 3474.20
ν3 νB νH (para) 3509.35
3
J12 = J45 JAC = JAĆ´ JHH (ortho) 8.01
4
J13 = J35 JAB = JA´B JHH (meta) 1.18
5
J14 = J25 JAB´ = JA´B JHH (para) 0.44
4
J15 JAA´ JHH (meta) 2.12
3
J23 = J34 JBC = JBĆ JHH (ortho) 7.42
4
J24 JCC´ JHH (meta) 1.76
HWB global 0.3 def.
Data from: K. Hayamizu, O. Yamamoto; J. Mol. Spec. 25, 422-435 (1968)
7.30 7.20 7.10 7.00

(ppm)
1
Figure 555 : 500 MHz H NMR spectrum of C6H5Br. [AC]2B system.
H146197_00_01
755
1
Expanded 500 MHz H NMR Spectrum of C6H5Br. Ortho-Protons Form A Part.
3656 3652 3648 3644 3640 3636

(Hz)
Figure 556 : Ortho-protons form A part. Observe the repeated spacings of 1.25 Hz ≈ J13 = JHH which
4
identify the ortho-protons!
List of Transition Frequencies and Intensities for Ortho-Protons

1 3654.4770 0.4411
2 3652.0188 0.5880
3 3651.9738 1.8867
4 3651.9508 1.8874
5 3651.6501 0.9049
6 3651.3089 0.9925
7 3650.9349 0.8049
8 3650.7318 1.9185
9 3650.7105 1.9191
10 3649.9045 1.4675
11 3649.7130 1.1248
12 3648.9959 1.3474
13 3645.7062 1.5391
14 3644.1450 1.0774
15 3643.9616 1.4301
16 3643.8038 0.9899
17 3643.6082 2.0757
18 3643.5868 2.0765
19 3643.3750 1.2112
20 3642.3429 2.1163
21 3642.3152 2.1175
22 3642.1531 0.8918
23 3641.1338 0.5133
24 3640.9386 0.6703
25 3614.5197 0.0012
26 3612.8715 0.0016
H146197_00_01
756
1
Expanded 500 MHz H NMR Spectrum of C6H5Br. Para-Proton Forms B Part
3520 3516 3512 3508 3504 3500

(Hz)
Figure 557 : Para-protons form B part. Observe the averaged triplet splittings of: 1.25 Hz ≈ J13 = JHH and
4
7.34 Hz ≈ J23 = JHH.

3
List of Transition Frequencies and Intensities for Para-Proton

1 3518.7024 0.6258
2 3518.5400 0.0043
3 3517.6589 0.0051
4 3517.4679 0.6457
5 3517.4605 0.6452
6 3516.2202 0.6684
7 3512.2274 0.8697
8 3510.5278 1.0174
9 3510.4827 0.8542
10 3510.1538 0.9799
11 3510.0990 0.8717
12 3509.7693 1.0096
13 3509.5741 0.8826
14 3508.1618 0.9828
15 3504.0527 1.5608
16 3502.7952 1.4795
17 3502.7811 1.4781
18 3502.5938 0.0192
19 3501.7120 0.0092
20 3501.5158 1.3953
H146197_00_01
757
1
Expanded 500 MHz H NMR Spectrum of C6H5Br. Meta-Protons Form C Part
3484 3480 3476 3472 3468 3464

(Hz)
Figure 558 : Meta-protons form C part. Observe the repeated spacings of 7.34 Hz ≈ J23 = JHH which
3
identify the meta-protons!
List of Transition Frequencies and Intensities for Meta-Protons

1 3483.7770 0.6240
2 3481.8654 2.6374
3 3481.2738 2.4875
4 3481.2437 1.3732
5 3481.0505 1.1893
6 3479.7460 1.9439
7 3476.0858 0.5313
8 3475.0062 1.7301
9 3474.7988 1.7057
10 3473.9399 0.6472
11 3473.7385 1.1052
12 3473.7364 0.9751
13 3473.6908 1.5567
14 3473.5454 1.1651
15 3473.4497 2.3176
16 3472.9599 2.2190
17 3472.0444 1.0572
18 3470.9752 0.5327
19 3468.0285 1.1126
20 3466.3800 0.8733
21 3466.3139 1.5877
22 3466.1765 0.6697
23 3465.3913 1.4884
24 3463.9871 0.4635
H146197_00_01
758
1
Compare the H NMR spectra of bromobenzene and chlorobenzene.
The 500 MHz [AB]2C spectrum of chlorobenzene is more difficult to analyze than the [AC]2B case
of bromobenzene. In such situations automated analysis using TopSpin / DAISY will help and
rapidly lead to converging solution.
7.12 7.08 7.04 7.00 6.96

(ppm)
1
Figure 559 : Simulated 500 MHz H NMR spectrum of chlorobenzene.
7.12 7.08 7.04 7.00 6.96

(ppm)
1
Figure 560 : Simulated 1000 MHz H NMR spectrum of chlorobenzene.
H146197_00_01
759
[AB]2C System in Chlorobenzene C6H5Cl

δ1 = δ5 δA = δA´ δH (ortho) 7.1319 [ppm]
δ2 = δ4 δB = δB´ δH (meta) 7.0046 [ppm]
δ3 δC δH (para) 6.9701 [ppm]

3
J12 = J45 JAB = JA´B´ JHH (ortho) 8.05 [Hz]
4
J13 = J35 JAC = JAĆ JHH (meta) 1.17 [Hz]
5
J14 = J25 JAB´ = JA´B JHH (para) 0.44 [Hz]
4
J15 JAA´ JHH (meta) 2.27 [Hz]
3
J23 = J34 JBC = JBC´ JHH (ortho) 7.46 [Hz]
4
J24 JBB´ JHH (meta) 1.27 [Hz]
HWB global 0.3 def. [Hz]
Data from: K. Hayamizu, O. Yamamoto; J. Mol. Spec. 25, 422-435 (1968).

Read: J. M. Read, Jr., H. H. Goldstein; J. Mol. Spec. 23, 179-190 (1967) on C6H5R (R = Cl, Br, I).
20.2 Spectra of C6H5R (R = H, CHO, F, 15N, CH3, CH=CH2)
Coupling between ring protons and spin active nuclei from substituent R of compounds C6H5R (R =
15
H, CHO, F, N, CH3, CH=CH2) introduce additional complexity.
Case A - R = H
Symmetry increases and the A6 singlet spectrum centered at νA of benzene C6H6 results. Coupling
3 4 5
constants JHH, JHH, and JHH are hidden in this 1D NMR spectrum but can be detected by several
13 1
techniques, e. g.: by inspection of the C satellites in the H NMR spectrum of the isotopomer:
H
13
H C H
H H
H
3 4 5
Analysis and iteration yielded JHH = 7.54 Hz, JHH = 1.37 Hz, and JHH = 0.69 Hz.
Read: J. M. Read Jr., R. E. Mayo, J. H. Goldstein; J. Mol. Spec. 22, 419-425 (1967).
H146197_00_01
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Case B - R = CHO
1 1
An [AC]2BX system is observed for benzaldehyde C6H5CHO. By H{ H} decoupling the aldehyde
proton CHO, the complexity of the [AC]2BX case was reduced to the more simple [AC]2B system,
which yielded the five-spin parameters by methods shown above.
Read: K. Hayamizu, O. Yamamoto; J. Mol. Spec. 28, 89-100 (1068).
Case C - R = F
The [CA]2BX system of monofluorobenzene C6H5F results. This problem was tackled by early
studies of S. Castellano, R. Kostelnik, C. Sun; Tetr. Lett. 46, 4635-4639 (1967). We will discuss the
[CA]2BX system in a subsequent chapter on a series of fluorinated benzenes C6H6-iFi (i = 1-7).
15
Case D - R = NO2
15 15
A meticulous study of the [AC]2BX system in N-substituted nitrobenzene C6H5 NO2 was
presented by L. Ernst, E. Ludwig, V. Wray, J. Magn. Res. 22, 459-466 (1976).
1 15 13
H, N, and C NMR spectra were measured using a 100 MHz spectrometer. NMR parameters of
[AC]2BX were iterated with LAOCOON III. Spin enumeration and numerical results are shown
below:
15
NO2 6 X
H H 1 5 A A´
H H 2 4 C C´
H 3 B
H146197_00_01
761
1
Data for Simulation of 100 MHz H NMR Spectrum
νi Type Type Data

1 and 5 H A and A´ 816.4382
2 and 4 H C and C´ 756.5190
3 H B 772.5870
15
6 N X 0 def.
Jik Data
3
12 and 45 JHH JAC and JAĆ´ 8.3130
4
13 and 35 JHH JAB and JA´B 1.1690
5
14 and 25 JHH JAC´ and JAĆ 0.4920
4
15 JHH JAC 2.4630
3
16 and 56 JNH JAX and JA´X -1.9360
3
23 and 34 JHH JBC and JBĆ 7.4680
4
24 JHH JCC´ 1.4800
4
26 and 46 JNH JCX and JC´X -0.8270
5
36 JNH JBX -0.2930
HWB
global 0.3 def.
15
Solvent: CD3-CO-CD3 / TMS 5:1. Concentration: 70% C6H5 NO2 in solvent.
1
Simulation of 100 MHz H NMR Spectrum
820 810 800 790 780 770 760 750

(Hz)
Figure 561 : Protons [AC]2B part from [AC]2BX at 100 MHz
H146197_00_01
762
2.5 1.0 -0.5 -2.0 -3.5

(Hz)
15
Figure 562 : Nitrogen N-, X part from [AC]2BX at 10.13 MHz
1
Simulation of 500 MHz H NMR Spectrum
4050 4000 3950 3900 3850 3800

(Hz)
Figure 563 : Protons - the [AC]2B part from [AC]2BX at 500 MHz
2.5 1.0 -0.5 -2.0 -3.5

(Hz)
15
Figure 564 : Nitrogen N, X part from [AC]2BX at 50.68 MHz
n
Evaluation of the X part leads to absolute values for JNH data. SPT experiments showed that signs
n
of all JNH were negative.
H146197_00_01
763
n
Coupling Constants JNH
3
16 and 56 JNH JAX and JA´X -1.936 Hz
4
26 and 46 JNH JCX and JC´X -0.827 Hz
5
36 JNH JBX -0.293 Hz
Case E - R = CH3
n
Benzylic couplings JHH (n = 4-6) are observed for this [BA]2CX3 system of toluene. Basically the
overlap of 4 [ba]2c sub-systems were observed in the [BA]2C region affiliated with statistical weights
4
1:3:3:1. (A less clean description would be a quartet of [ba]2c sub-spectra). Results: JHH = -0.746
5 6
Hz, JHH = 0.356 Hz, JHH = -0.619 Hz.
1
A Meticulous Reinvestigation at 300.135 MHz Yielded H NMR Data [Hz]:
νi Type Type Data [Hz]

1 and 5 H B and B´ 2106,558
2 and 4 H A and A´ 2130,281
3 H C 2102.784
6 CH3 X3 688,561
Jik Data [Hz]
3
12 and 45 JHH JAB and JA´B´ 7.655
4
13 and 35 JHH JBC and JBĆ 1.273
5
14 and 25 JHH JAB´ and JA´B 0.610
4
15 JHH JBB´ 1.902
4
16 and 56 JHH JBX and JB´X -0.702
3
23 and 34 JHH JAC and JAĆ 7.417
4
24 JHH JAA´ 1.442
5
26 and 46 JHH JAX and JA´X 0.329
6
36 JHH JCX -0.602
n
Remember: The sign of a benzylic coupling constant JHH is negative for even n and positive for
uneven n.
Read:
a) M. P. Williamson, R. J. Kostelnik, S. M. Castellano; J. Chem. Phys. 49, 2218-2224 (1968).
b) T. Schaefer, R. Sebastian, G.H. Penner; Can. J. Chem. 63, 2597-2599 (1985)
H146197_00_01
764
Case F - R = CH=CH2
1
In a starting phase the 200 MHz H NMR spectrum of styrene in CDCl3 may be handled as
superposition of two fragments: the phenyl unit ([AB]2C type) and the vinyl unit (XYZ type,
corresponding to the general ABC type).Iteration with DAISY using suitable starting parameters
and nuclei specific line widths yielded an acceptable fit - at first sight:
The Phenyl Part
[AB]2C Data [Hz]

νA 1480.920
νB 1463.445
νc 1449.120
JAB 7.863
JAC´ 1.195
JAB´ 0.356
JAA´ 2.064
JBC 7.440
JBB´ 1.516
HWB (A) 0.838
HWB (B) 0.680
HWB (C) 0.616
All errors are smaller than 0.02 Hz.
The Vinyl Part
XYZ Data [Hz]
νX 1343.078
νY 1149.087
νZ 1047.371
JXY 17.612
JXZ 10.897
JYZ 0.953
HWB (global) 0.693
All errors smaller than 0.002 Hz.
H146197_00_01
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1
Figure 565 : 200 MHz H NMR spectrum of styrene in CDCl3 + TMS. Upper: experimental, lower:
iterated.
Data for chemical shifts and coupling constants inside those two fragments C6H5 and CH2=CH
seemed consistent with results from analogous compounds and hence agreeable. But the spectral
half width HWB for nuclei X, Y and Z appeared slightly too large and not due to bad resolution by
shimming errors. Long range couplings between the C6H5 and CH2=CH groups might give rise to
this apparent line width effect. And this is true, as will be shown in the next section.
One Step Closer to Perfection – the 270 MHz 1H NMR Spectrum of Styrene
1
A meticulous study showed that the total H NMR spectrum of styrene should not be handled by
n
two separated 5- and 3-spin fragments [AB]2C and XYZ resp. Long range couplings JHH (n = 5 to
7) were observed combining both units to a total 8 spin case described as [AB]2CDEF system
approximating the [AB]2CXYZ case.
H146197_00_01
766
H 1 F
H 3 D
H 2 E
H H 4 5 A A´
H H 6 7 B B´
H 8 C
7.2 6.8 6.4 6.0 5.6 5.2

(ppm)
1
Figure 566 : 270 MHz H NMR spectrum of styrene
7.44 7.40 7.36 7.32 7.28 7.24 7.20

(ppm)
1
Figure 567 : Phenyl part from 270 MHz H NMR spectrum of styrene – protons [AB]2C
H146197_00_01
767
6.76 6.72 6.68 6

1
Figure 568 : Vinyl part from 270 MHz H NMR spectrum of styrene – proton D
5.80 5.76 5.72
1
Figure 569 : Vinyl part from 270 MHz H NMR spectrum of styrene – proton E
5.24 5.20 5.16
1
Figure 570 : Vinyl part from 270 MHz H NMR spectrum of styrene – proton F
H146197_00_01
768
Corresponding Data are Listed in the Following Table:
δi Type Data
1 F 1402.922
2 E 1556.552
3 D 1813.593
4 and 5 A and A´ 2002.593
6 and 7 B and B´ 1968.843
8 C 1949.403
Jik Data
2
12 JHH EF 1.054
3
13 JHH cis DF 10.941
5
14 and 15 JHH AF and A´F 0.1580
6
16 and 17 JHH BF and B´F 0
7
18 JHH CF 0.281
3
23 JHH trans DE 17.652
5
24 and 25 JHH AE and AÉ 0
6
26 and 27 JHH BE and BÉ 0
7
28 JHH CE 0.237
4
34 and 35 JHH AD and A´D -0.525
5
36 and 37 JHH BD and B´D 0.368
6
38 JHH CD -0.227
4
45 JHH meta AA´ 1.905
3
46 and 57 JHH ortho AB and A´B´ 7.791
5
47 and 56 JHH para AB´ and A´B 0.597
4
48 an d 58 JHH meta AC and AĆ 1.243
4
67 JHH meta BB´ 1.422
3
68 and 78 JHH ortho BC and BĆ 7.445
HWB global 0.08
Long range couplings are indicated blue.
This excellent study is based upon the following experimental conditions: Concentration: 2 mol /
liter styrene in solvent mixture CD3COCD3 / TMS 9:1. Temperature: 25°C. Sample was sealed
under vacuum (freeze - pump - thaw technique). Digital resolution: 0.058 Hz / point. Line width 0.08
1
Hz! 270 MHz H NMR using a Bruker WP 270 spectrometer.
Iteration by LACX, a program based upon frequency iteration.
H146197_00_01
769
Spin assignments were confirmed by comparing results obtained from α-D-styrene:
D
H
H H
H H
Read: H. Nies, H. Bauer, K. Roth, D. Rewicki; J. Magn. Res. 39, 521-524 (1980).
Case G - R = C6H5
If no cross ring couplings exist or are not taken into account, an [AB]2C system suffices to describe
1
the H NMR spectrum of biphenyl:
7.56 7.52 7.48 7.44 7.40 7.36 7.32

(ppm)
1
Figure 571 : Simulated 400 MHz H NMR spectrum of biphenyl, ca. 2 mol% in CDCl3. [AB]2C model.
H146197_00_01
770
1
400 MHz H NMR Spectral Data from Biphenyl, ca. 2 Mol% in CDCl3.
δi Data
1=5 7.577
2=4 7.414
3 7.321
Jik Data
12 =45 7.79
13 = 35 1.24
14 = 25 0.59
15 2.03
23 = 34 7.45
24 1.39
HWB 0.3
Data from: M. Yanagisawa, K. Hayamizu; Magn. Res. Chem. 25, 184-186 (1987)
Including cross ring couplings between both phenyl ring systems lead to a more complex 10 spin
problem, the [[AB]2C]2 case.
2 1 6 7
3 8
4 5 10 9
5
A simplified model uses the following cross ring couplings: JHH between protons
(1,6) = (1,10) = (5,6) = (5,10).
H146197_00_01
771
5
In a didactical series JHH was set to 0, 0.25, and 0.5 Hz to simulate the following plots:
5
Cross Ring Coupling JHH and Line Shape
7.56 7.52 7.48 7.44 7.40 7.36 7.32
7.56 7.52 7.48 7.44 7.40 7.36 7.32
7.56 7.52 7.48 7.44 7.40 7.36 7.32

(ppm)
1
Figure 572 : Simulated 400 MHz H NMR spectrum of biphenyl, ca. 2 mol% in CDCl3.
5
Upper trace: Cross ring couplings JHH = 0, corresponding to [AB]2C model. Middle trace: Cross
5 5
ring coupling JHH = 0.25 Hz. Lower trace: Cross ring coupling JHH = 0.5 Hz. The latter two cases
were calculated with DAISY using symmetry simplifications for faster simulations of [[AB]2C]2
model.
Note: Cross ring couplings may be overlooked in practice and line shapes misinterpreted by
broader line width.
Case H - R = OOC-C6H5 and R = C6H5-COO
1
Overlapping [AC]2B and [CA]2B Spectra in H NMR Spectra of Phenylbenzoate.
1
No cross ring couplings are observed for C6H5-COO-C6H5. H NMR spectra of phenylbenzoate
consist of two independent fragments, the benzoic and the phenolic parts.
H146197_00_01
772
H4 H5 H5 H4
m o O o m
H3 p i
C O i p
H3
m o o m
H2 H1 H1 H2
1
Figure 573 : 500 MHz H NMR spectrum of phenylbenzoate in CDCl3.
Fragment specific assignments are achieved using 2D NMR techniques.
HH COSY (Figure 574 :) identifies two separate [AC]2B and [CA]2B type spectra but does not
correlate the A- and C-resonances specifically to ortho- and meta-protons resp.
An additional HSQC spectrum (Figure 575 :) correlates proton- and carbon-resonances.
13 1
A corresponding 1D C{ H} NMR spectrum (Figure 576 :) is well understood by comparing
assignments for C6H5COOCH3 and CH3COOC6H5 with those of C6H5COOC6H5.
H146197_00_01
773
Hence resonances for protons in phenylbenzoate are identified specifically as shown in the next
figures.
Spin Assignment
Figure 574 : Assignment of C6H5-COO-C6H5 by HH COSY
Figure 575 : Assignment of C6H5-COO-C6H5 by HSQC
H146197_00_01
774
13 1
C{ H} NMR Spectrum of C6H5-COO-C6H5
13 1
Figure 576 : C{ H} NMR spectrum of C6H5-COO-C6H5
Chemical Shifts δC from C6H5-COO-C6H5 (in CDCl3).
C6H5-COO-C6H5 C6H5-COO-C6H5
Benzoic part Phenolic part
Line Carbon Shift Line Carbon Shift
1 COO 165.2012
3 para 133.5827 2 ipso 151.0144
4 ortho 130.4944 6 meta 129.5058
5 ipso 129.6452 8 para 125.8966
7 meta 128.5853 9 ortho 121.7351
13
Comparison with methylbenzoate and phenylacetate assigned the C resonances:
Chemical Shifts δC from C6H5-COO-CH3 and CH3-COO-C6H5 (in CDCl3).
C6H5-COO-CH3 CH3-COO-C6H5
Line Carbon Shift Line Carbon Shift
1 COO 166.99 1 COO 169.35
2 para 132.82 2 ipso 150.62
3 ortho 130.21 3 meta 129.34
4 ipso 129.53 4 para 125.74
5 meta 128.30 5 ortho 121.51
Data for C6H5-COO-CH3 and CH3-COO-C6H5 from: C. J. Pouchet and J. Benke. "The Aldrich
13 1
Library of C and H FT NMR Spectra". Edition I. Volume 2. No. 1240/A and No. 1285/B. Aldrich
Chemical Company Inc. 1993.
H146197_00_01
775
1
After having assigned the ortho-, meta- and para-protons in C6H5-COO-C6H5 the H NMR spectrum
was iterated successfully:
8.2 8.0 7.8 7.6 7.4 7.2

(ppm)
1
Figure 577 : 500 MHz H NMR total spectrum. Upper: experimental. Lower: simulated after iteration.
1
Iterating the 500 MHz H NMR Spectrum of C6H5-COO-C6H5 - Part I
Spins Type Benzoic Part Type Phenolic Part Type

[AC]2B [CA]2B
1, 5 δH(ortho) 8.2819 A 7.2708 C
2, 4 δH(meta) 7.5648 C 7.4819 A
3 δH(para) 7.6859 B 7.32 B
1, 5 νH(ortho) 4130.94 A 3635.39 C
2, 4 νH(meta) 3782.41 C 3740.96 A
3 νH(para) 3842.97 B 3662.17 B
H146197_00_01
776
1
Iterating the 500 MHz H NMR Spectrum of C6H5-COO-C6H5 - Part II
Spins Type Benzoic Part Type Phenolic Part Type

[AC]2B [CA]2B
3
12, 45 JHH 7.85 AC 8.1 AC
4
13, 35 JHH 1.32 AB 1.16 BC
5
14, 25 JHH 0.62 AC´ 0.46 AC´
4
15 JHH 1.88 AA´ 2.51 CC´
3
23, 34 JHH 7.43 BC 7.46 AB
4
24 JHH 1.35 CC´ 1.73 AA´
1, 5 HWB(ortho) 0.53 0.54
2,4 HWB(meta) 0.55 0.54
3 HWB(para) 0.57 0.57
An additional peak at 7.293 ppm with a statistical weight of 0.3 is due to traces of CHCl3 in solvent
CDCl3. HWB = 0.5 Hz.
Expanded Spectra
28 8.26 8.24
(ppm)
1
Figure 578 : Expanded 500 MHz H NMR spectrum. Benzoic part. Ortho-protons.
H146197_00_01
777
7.70 7.68 7.66 7

(ppm)
1
Figure 579 : Expanded 500 MHz H NMR spectrum. Benzoic part. Para-proton.
7.60 7.58 7.56 7.54 7.52

(ppm)
1
Figure 580 : Expanded 500 MHz H NMR spectrum. Benzoic part. Meta-protons.
H146197_00_01
778
7.50 7.48 7.46 7.4

(ppm)
1
Figure 581 : Expanded 500 MHz H NMR spectrum. Phenolic part. Meta-protons.
7.34 7.32 7.30 7.28 7.26 7.24

(ppm)
1
Figure 582 : Expanded 500 MHz H NMR spectrum. Phenolic part. Para-proton.
CHCl3 (7.293 ppm) from solvent CDCl3. Phenolic part. Meta-protons.
H146197_00_01
779
1
Do we Need 2D NMR to Analyze the H NMR Spectrum of 2-Benzoylpyridine?
2-Benzoylpyridine is characterized by two fragments corresponding to an [AC]2B system from the
benzoyl part and an ABCD system from the pyridyl unit:
1
H NMR spectra of this model compound are excellent examples to run TopSpin / DAISY
calculations using fragmentation techniques.
1
S. Castellano and A. A: Bothner-By analyzed the 60 MHz H NMR spectrum of 2-benzoylpyridine:
8.6 8.4 8.2 8.0 7.8 7.6 7.4 7.2

(ppm)
1
Figure 583 : Simulated 60 MHz H NMR spectrum of 2-benzoylpyridine
and determined resonance frequencies and coupling constants by iteration with the frequency-
based program LAOCOON II. Spectrum and theoretical background of calculations are described
in an interesting publication: "Analysis of NMR Spectra by Least Squares" from S. Castellano, A. A.
Bothner-By; J. Chem. Phys. 41, 3863-3869 (1964).
H146197_00_01
780
Using those 60 MHz data from Castellano and Bothner-By a corresponding 500 MHz spectrum was
simulated.
1
Figure 584 : Simulated 500 MHz H NMR spectrum of 2-benzoyl-pyridine. Oversight.
Seven signals are detected, where signals 1, 3, 4, 5 and 6 correspond to one proton while signals 2
and 5 each correspond to a pair of protons. Bearing in mind the characteristic spectral pattern of
[AC]2B system signals 2, 5 and 6 and are assigned to A, C and B type protons of the phenyl group.
Signals 1, 3, 4 and 7 belong to the 2-pyridyl group which is responsible for an AMRX type system
with weak ABCD character.
Hence the total spectrum shown above is divided in two fragments:
8.6 8.4 8.2 8.0 7.8 7.6 7.4

(ppm)
2 5 6
1
Figure 585 : Simulated 500 MHz H NMR spectrum of 2-benzoyl-pyridine. [AC]2B part.
H146197_00_01
781
8.6 8.4 8.2 8.0 7.8 7.6 7.4

(ppm)
1 3 4 7
1
Figure 586 : Simulated 500 MHz H NMR spectrum of 2-benzoyl-pyridine. ABCD part.
This assignment is verified by inspection of the expanded spectrum:
4070 4065 4060 4055 4050 4045

(Hz)
Figure 587 : Signal 2 - Benzoyl fragment 1 - Protons 1 and 5 - A, A´
3745 3740 3735 3730 3725 3720 3715

(Hz)
Figure 588 : Signal 5 - Benzoyl Fragment 1 - Proton 3 - B
H146197_00_01
782
3700 3695 3690 3685 3680 3675 3670

(Hz)
Figure 589 : Signal 6 - Benzoyl Fragment 1 - Protons 2 and 4 - C, C´
Find repeated spacings in these spectral parts.
4295 4290 4285 4280 4275

(Hz)
Figure 590 : Signal 1 - Pyridyl fragment 2 - Proton 1 - A
3990 3985 3980 3975 3970 3965

(Hz)
Figure 591 : Signal 3 - Pyridyl fragment 2 - Proton 4 - B
H146197_00_01
783
3875 3870 3865 3860 3855 3850 3

(Hz)
Figure 592 : Signal 4 - Pyridyl Fragment 2 - Proton 3 - C
3665 3660 3655 3650 3645 3640 3635

(Hz)
Figure 593 : Signal 7 - Pyridyl Fragment 2 - Proton 2 - D
H146197_00_01
784
1
H NMR Data for 2-Benzoyl-pyridine Used for Simulation
Benzoyl Fragment - [AC]2B system
δi Shift
1=5 A, A´ 8.1150 ppm
2=4 C, C´ 7.3722 ppm
3 B 7.4605 ppm
νi Frequencies
1=5 A, A´ 4057.50 Hz
2=4 C, C´ 3686.10 Hz
3 B 3730.25 Hz
Jik Couplings
3
12 = 45 AC JHH 7.90 Hz
4
13 = 35 AB JHH 1.34 Hz
5
14 = 25 AC´ JHH 0.59 Hz
4
15 AA´ JHH 1.73 Hz
3
23 = 34 BC, BC´ JHH 7.44 Hz
4
24 CC´ JHH 1.30 Hz
Global HWB 0.30 Hz
Lines calc. 68
Pyridine Fragment - ABCD System
δi Shifts
1 A 8.5685 ppm
2 D 7.2997 ppm
3 C 7.7210 ppm
4 B 7.9552 ppm
νi Frequencies
1 A 4284.25 Hz
2 D 3649.85 Hz
3 C 3860.50 Hz
4 B 3977.61 Hz
Jik Couplings
3
12 AD JHH 4.76 Hz
4
13 AC JHH 1.77 Hz
5
14 AB JHH 0.93 Hz
3
23 CD JHH 7.58 Hz
4
24 BD JHH 1.24 Hz
3
34 BC JHH 7.88 Hz
Global HWB 0.30 Hz
Lines calc. 32
Extrapolated from 60 MHz analysis by S. Castellano, A. A. Bothner-By; J. Chem. Phys. 41, 3863-
3869 (1964). Resonance frequencies were converted to 500 MHz. A global half width was
arbitrarily set to 0.3 Hz.
H146197_00_01
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While the assignment of phenyl protons to [AC]2B in 2-benzoyl-pyridine is unique, the ABCD
1
problem from the pyridyl ring might have a complimentary solution. 1D H NMR may assign protons
(1,2,3,4) either to spins ADCB or to BCDA:
How do we find the true solution to the ABCD problem? Chemical shift prediction or HC-COSY will
solve the problem.
1
But a simpler solution is derived by comparison of H NMR spectra of structurally related
compounds:
H 3 B
H H 2 4 C C´
H N H 1 N 5 A N A´
Pyridine
8.6 8.4 8.2 8.0 7.8 7.6 7.4 7.2 7.0

(ppm)
1
Figure 594 : Simulated 500 MHz H NMR spectrum of pyridine (10% in CCl4). [AC]2B type.
H146197_00_01
786
NMR Data for Pyridine (10% in CCl4) Used for 500 MHz Simulation
δi
1=5 ortho A, A´ 8.6085
2 =4 meta C, C´ 7.1551
3 para B 7.5018
νi
1=5 ortho A, A´ 4262.15
2 =4 meta C, C´ 3577.60
3 para B 3770.00
Jik
3
12 = 45 JHH AC = AĆ´ 4.862
4
13 = 35 JHH AB = A´B´ 1.850
5
14 = 25 JHH AC´ = AĆ 0.984
4
15 JHH AA´ -0.128
3
23 = 34 JHH BC = BĆ´ 7.656
4
24 JHH CC´ 1.360
global HWB 0.300

nL 68
Extrapolated from 60 MHz Analysis by S. Castellano, A. A. Bothner-By; J. Chem. Phys. 46, 327-
330 (1967). Resonance frequencies were converted to 500 MHz. Global half width set to 0.3 Hz.
Significant parameters: δH (A) > δH (B) and 3JHH (AC) > 3JHH (BC)
Neighborhood effects of nitrogen increase the chemical shift of the ortho-proton (H1, HA) and
3 3
decrease the ortho coupling constant JHH (AC) to 4.862 Hz, while the ortho coupling constant JHH
(BC) is larger with = 7.656 Hz and falls into the range of normal ortho couplings from aromatic
phenyl units.
H146197_00_01
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Corresponding findings are true for substituted pyridines like 2-picolinic acid or 2-(pyridin-2-yl)-1H-
benzo[d]imidazole which give rise to ABCD type spectra:
H 3 C
H H 2 4 D B
H N R 1 N R A N R
H H
N H
1 R= COOH 2 R= C
N H
2-Picolinic acid 2-(Pyridin-2-yl)-1H-benzo[d]imidazole
The following parameters were determined for 2-(pyridin-2-yl)-1H-benzo[d]imidazole:
H1 H2 H3 H4
δH 8.82 7.60 8.11 8.51 ppm
HA HD HC HB
and an analogous assignment is found for 2-picolinic acid.

Hence we note:
δH (H1) > δH (H4) > δH (H3) > δH (H2) and δH (HA) > δH (HB) > δH (HC) > δH (HD)
Those results confirm the assignment of spins claimed in the early investigations on 2-benzoyl-
pyridine by Castellano and Bothner-By discussed above.
Read: "Variable-temperature NMR studies of 2-(pyridin-2-yl)-1H-benzo[d]imidazole" by A. Yeh, C.-

Y. Shih, L.-L. Lin, S.-J. Yang, C.-T. Chang; Life Science Journal, Vol. 6, No. 4, 2009.
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A Final Check - the 200 MHz 1H NMR Spectrum of 2-Benzoylpyridine
A 0.1 % solution of 2-Benzoylpyridine in a solvent mixture CCl4/CD3COCD3 (9:1) was made and
1
traces of TMS were added as internal reference for 200 MHz H NMR. An extended and automated
spectral analysis involving nuclear specific line widths was performed with DAISY leading to the
following results:
Benzoyl fragment Pyridyl fragment

Parameter Data Type Parameter Data Type
δH (Hi) [ppm] δH (Hi) [ppm]
1=5 8.2478 A 1 8.8251 A
2=4 7.6219 C 2 7.7023 D
3 7.7321 B 3 8.1180 C
4 8.1608 B
νH (Hi) [Hz] νH (Hi) [Hz]
1=5 1649.5600 1 1765.0200
2=4 1524.3800 2 1540.4600
3 1546.4200 3 1623.6000
4 1632.1600
Jik [Hz] Jik [Hz]
12 = 45 7.8614 12 4.7551
13 = 35 1.3402 13 1.7889
14 = 25 0.6417 14 0.9422
15 1.8341 23 7.6367
23 = 34 7.4665 24 1.2841
24 1.4478 34 7.8745
HWB (Hi) [Hz] HWB (Hi) [Hz]
1=5 0.6761 1 0.9043
2=4 0.7102 2 0.6374
3 0.6851 3 0.6502
4 0.6903
Results from: Robert Spiske, PhD Thesis 1996, Heinrich Heine University Düsseldorf.
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Corresponding plots for total spectrum, benzoyl and pyridyl fragment are given below:
8.8 8.6 8.4 8.2 8.0 7.8 7.6

(ppm)
1
Figure 595 : Simulated 200 MHz H NMR spectrum of 2-benzoylpyridine
8.8 8.6 8.4 8.2 8.0 7.8 7.6

(ppm)
Figure 596 : The benzoyl fragment
8.8 8.6 8.4 8.2 8.0 7.8 7.6

(ppm)
Figure 597 : The pyridyl fragment
H146197_00_01
790
Coupling constants found are consistent with results from Castellano and Bothner-By. A
remarkable solvent effect on chemical shifts is detected. Addition of acetone-d6 induces individual
low-field shifts for all the resonance frequencies of both fragments. Furthermore, the quadrupolar
14
N gives rise to a selective increase of the spectral half width for the low field proton H1 = HA from
the pyridyl fragment. This observation is an additional confirmation for the spectral assignment
shown below:
19
20.3 F NMR Spectra of Pentafluorophenyl Groups in C6F5R
Compounds
R R
F F 5 1
F F 4 2
F 3
19 19
F chemical shifts depend strongly on substituent effects. In practice C6F5 groups give rise to F
NMR spectra of [AC]2B or [CA]2B type which approximate [AX]2M or [XA]2M cases. Hence it is
19 1
easier to analyze F NMR spectra from C6F5R than analogous H NMR spectra from
corresponding C6H5R compounds.
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791
Spin System Substituent R in Compounds C6F5R

-H, -BF2, -BCl2, -CH3, -CF3, -CH2OH, -CH2Br, -C2H5, -CN, -C6F5,
-CH=CH2, -C≡CH, -C6H5, -CHO, -COOH, -COOC2H5, -COF, -COCl,
+
[AC]2B -COCH3, -COC6F5, -Si(CH3)3, -Sn(CH3)3, -Pb(C6F5)3, -NH3 ,
-N(CF3)2, -NO2, -P(CH3)2, -P[N(CH3)2]2, -PF2, -P(O)F2, -OH, -OCH3,
-SH, -SD, -SCH3, -SCl, -SCN, -SF3, -SOF, -SO2F, -SO2Cl, -Cl, -Br, -I
- -
[AB]2C -NH2, -NHCH3, -N(CH3)2, -NHNH2, -OH, -O , -OSi(CH3)3, -S , -HgCH3
Chemical shifts δF and coupling constants JFF are influenced by substituent effects. Empirical
n
correlations were found between JFF and δF of para-fluorine, e. g.

n
δF para
4
J13 ↑ if ↑ more sensitive
δF para
5
J14 ↑ if ↑ less sensitive
δF para
4
J15 ↓ if ↑ more sensitive
δF para
4
J24 ↑ if ↑ less sensitive
4 4
This symbolic representation implies: J13 increases (while J15 decreases) significantly with
increasing δF (F3). In contrast hereto J14 (and J24) increases less significantly with increasing δF
5 4
(F3).
For details read: E. A. Cohen, A. J. R. Bourn and S. L. Mannat, J. Magn. Res. 1, 436-449 (1969)
20.3.1 Example 1: The 470.385 MHz 19F NMR Spectrum of C6F5Br
Br Br
F F 5 1
F F 4 2
F 3
H146197_00_01
792
30 25 20 15 10 5 0
(ppm)
19
Figure 598 : Simulated 470.385 MHz F NMR spectrum of C6F5Br.
19
470.385 MHz F NMR Data of C6F5Br
ν1 = ν 5 νF (ortho-F) 14138.1268
ν2 = ν 4 νF (meta-F) 899.1880
ν3 νF (para-F) 3707.7157
3
J12 = J45 JFF -21.4700
4
J13 = J35 JFF 1.2200
5
J14 = J25 JFF 6.2800
4
J15 JFF -5.3000
3
J23 = J34 JFF -19.6200
4
J24 JFF -1.6500
HWB global 0.3
All coupling constants and differences of resonance frequencies from V. Wray, J. Chem. Soc.
Perkin II, 1978, 855-861. Chemical shift of para-fluorine set according to E. A. Cohen, A. J. R.
Bourn and S. S. Manatt; J. Magn. Res. 1, 436-449 (1969) quoted by V. Wray.
H146197_00_01
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19
Expanded F NMR Spectrum of Ortho-Fluorines
14160 14145 14130 14115

(Hz)
Figure 599 : Ortho-fluorines
Transition Frequency Intensity

1 14156.4766 0.7572
2 14155.3422 0.7529
3 14154.6096 0.8650
4 14153.3122 0.8700
5 14150.8909 1.1306
6 14149.7305 1.1261
7 14149.5954 1.2385
8 14148.3240 1.2433
9 14146.3462 1.9975
10 14146.3359 1.9975
11 14145.1264 1.9979
12 14145.1162 1.9979
13 14131.1563 2.0021
14 14131.1462 2.0021
15 14129.9366 2.0025
16 14129.9264 2.0025
17 14127.8865 1.2426
18 14126.7188 1.2474
19 14126.6119 1.1348
20 14125.3323 1.1302
21 14122.8931 0.8692
22 14121.7506 0.8742
23 14121.0053 0.7613
24 14119.7006 0.7569
H146197_00_01
794
19
Expanded F NMR Spectrum of Para-Fluorines
3740 3730 3720 3710 3700 3690 3680

(Hz)
Figure 600 : Para-fluorines

1 3728.6237 0.9864
2 3727.4040 0.9861
3 3727.4038 0.9861
4 3726.1841 0.9858
5 3709.0723 1.0001
6 3708.9356 1.0002
7 3707.8008 0.9998
8 3707.7931 1.0000
9 3707.7752 0.9998
10 3707.7675 1.0000
11 3706.6331 0.9996
12 3706.4957 0.9998
13 3689.3842 1.0142
14 3688.1645 1.0140
15 3688.1643 1.0140
16 3686.9446 1.0139
H146197_00_01
795
19
Expanded F NMR Spectrum of Meta-Fluorines
930 920 910 900 890 880 870

(Hz)
Figure 601 : Meta-fluorines

1 926.7461 0.7621
2 924.7637 0.8802
3 921.1143 1.1380
4 919.7958 1.2560
5 916.5780 2.0164
6 916.5201 2.0162
7 907.1098 0.7560
8 905.1530 0.8631
9 901.5034 1.1270
10 901.3982 2.0117
11 901.3203 2.0115
12 900.1593 1.2340
13 898.1228 1.2518
14 896.9691 1.9883
15 896.8895 1.9882
16 896.7839 1.1338
17 893.1344 0.8759
18 891.1724 0.7580
19 881.7689 1.9839
20 881.7101 1.9837
21 878.5197 1.2301
22 877.1552 1.1228
23 873.5057 0.8591
24 871.5692 0.7520
19
Remember those spectral patterns. F NMR spectra of many other C6F5R appear with similar
patterns.
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20.3.2 Example 2: Pentafluorobenzene C6F5H – the Case of an [AC]2BX

Spectrum
H 1 H
F F 6 2 A´ A
F F 5 3 C´ C
F 4 B
19
Simulated 94 MHz F NMR spectrum of C6F5H using data shown below. Global spectral line width
arbitrarily set to 0.3 Hz and used for plotting.
-430 -440 -450 -460 -470 -4

(Hz)
Figure 602 : Ortho-fluorines
H146197_00_01
797
-1875 -1890 -1905 -1920

(Hz)
Figure 603 : Para-fluorine
-2670 -2685 -2700 -2715

(Hz)
Figure 604 : Meta-fluorines
730 725 720 715 710 705 700 695

(Hz)
1
Figure 605 : Simulated 100 MHz H NMR spectrum of C6F5H using data shown below.
H146197_00_01
798
1 19
100 MHz H NMR and 94.1 MHz F NMR data for C6F5H are marked bold when used for plots
shown above.
a) b)
Parameter Type Ref Ref
δi [ppm] [ppm]
1 H - 7.14
2=6 F -4.7983 -
3=5 F -28.5880 -
4 F 20.1409 -
νi [Hz] [Hz]
1 H - 714.00
2=6 F -451.52 -
3=5 F -2690.13 -
4 F -1895.26 -
Jik [Hz] [Hz]
3
12 = 16 JFH 10.21 10.416
4
13 = 15 JFH 6.87 7.004
5
14 JFH -2.67 -2.656
3
23 = 56 JFF -19.96 -20.565
5
24 = 46 JFF 1.33 1.213
4
25 = 36 JFF 8.87 8.782
4
26 JFF -2.37 -2.041
3
34 = 45 JFF -18.18 -18.747
4
35 JFF -1.11 -1.230
a) int. ref. TMS and C4F8. E. Lustig, P. Diehl, B. Bodmer; J. Chem. Phys. 49, 4550-4555
(1968). Note: Chemical shifts δF and resonance frequencies νF are referenced vs.
octafluo-rocyclubutane.
1 19
b) 75 % in CD3COCD3, int. ref TMS. 100 MHz H NMR, 94.1 MHz F NMR. V. Wray, L. Ernst,
E. Lustig; J. Magn. Res. 27, 1-21 (1977).
Study the 94.1 / 100 MHz [AC]2BX simulations shown above approximating an [AR]2MX situation.
Hence measurements at higher fields will not improve accuracy of NMR parameters. Analysis of
those patterns is straight forward: Find δH, JFH, JFH, JFH directly from the H NMR spectrum and
3 4 5 1
further δF(para), JFF, JFF, JFH from the F NMR spectrum of the para-fluorine spin. Ortho and
3 4 5 19
meta-fluorines give rise to 4 sub-spectra of [ac]2 / [mr]2 character centered symmetrically around
δF(ortho) and δF(meta) resp. Do the [mr]2 type analysis (corresponding to the well known [ax]2
case) or use expectation values for the missing coupling constants. Then subsequent iterations will
converge rapidly.
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20.3.3 Long Range Coupling between Fluorines in C6F5 and Spins in

Substituent R
20.3.3.1 Example 1: Perfluorotoluene. R = CF3. [AC]2BX3.
CF3 6
F F 5 1
F F 4 2
F 3
δ1 = δ5 δF (ortho-F) -140.28
δ2 = ν4 δF (meta-F) -161.06
δ3 δF (para-F) -148.37
3
J12 = J45 JFF -20.01
4
J13 = J35 JFF +5.54
5
J14 = J25 JFF +8.34
4
J15 JFF -7.52
3
J23 = J34 JFF -18.97
4
J24 JFF -0.43
δ6 δF (R) -56.49
4
J16 = J56 JFF +22.68
5
J26 = J46 JFF +0.62
6
J36 JFF +1.33
HWB global HWB global
Data from: C. W. Haigh, J. Hilton, L. H. Sutcliffe and G. J. T. Tiddy; J. Magn. Res. 18, 241-247
(1975).
Note: Benzylic couplings are larger in perfluorotoluene C6F5CF3 than in toluene C6H5CH3.
H146197_00_01
800
20.3.3.2 Example 2: Trimethylsilylpentafluorobenzene. R = Si(CH3)3. [AC]2BX9.
Si(CH3)3 6
F F 5 1
F F 4 2
F 3
δ1 = δ5 δF (ortho-F) -127.97
δ2 = ν4 δF (meta-F) -162.37
δ3 δF (para-F) -150.62
3
J12 = J45 JFF -24.63
4
J13 = J35 JFF +3.40
5
J14 = J25 JFF +10.12
4
J15 JFF -4.37
3
J23 = J34 JFF -19.75
4
J24 JFF -1.17
δ6 δH (R) 0.57
5
J16 = J56 JFH 1.58
6
J26 = J46 JFH 0
7
J36 JFH 0
Data from: G. Hägele and M. Weidenbruch

a) Chem. Ber. 106. 460-470 (1973),
b) Org. Magn. Res. 6, 66-77 (1974).
5
Note: Long range couplings JFH are observed between ortho-fluorines and protons from -
6
Si(CH3)3 in C6F5Si(CH3)3 (1.58 Hz) and -Si(CH3)2- in C6F5-Si(CH3)2-Si(CH3)3 (1.68 Hz). JFH is
observed between ortho-fluorines and protons from -Si(CH3)3 in C6F5-Si(CH3)2-Si(CH3)3 (0.65 Hz).
1
Corresponding H NMR signals appear as deceptively simple triplets.
6
Inter-annular long range couplings JFF between ortho-fluorines of pentafluorophenyl units are
detected for compounds like (C6F5)nSiR4-n (e. g. R = F, Cl, Br, CH3). The skeleton of (C6F5)nSi gives
H146197_00_01
801
rise to complex [[AC]2B]n type spectra. Increasing n will strongly affect the spectral pattern of
ortho-fluorines and to a lesser degree the patterns for meta- and para-fluorines.
C6F5SiBr3 (C6F5)2SiBr2 (C6F5)3SiBr
C6F5Si(CH3)3 (C6F5)2Si(CH3)2 (C6F5)3SiCH3
19
Figure 606 : 94.1 MHz F NMR: Comparing parts for ortho-fluorines in (C6F5)nSiR4-n.
A full analysis of such systems is beyond the scope of this manuscript. This is true for
n
perfluorobiphenyl C6F5-C6F5 as well, where inter-annular couplings JFF give rise to a very
complex [[AC]2B]2 spectrum.
19
Remember: F NMR spectra of pentafluorophenyl substituted compounds M(C6F5)nR4-n for n > 1
6
are complex due to inter-annular long range (through space) couplings JFF between ortho-fluorine
atoms of separate pentafluorophenyl rings. Broadened signals are monitored for fluorines in ortho,
meta and in para positions. The most complex situation is found for tetrakis(pentafluorophenyl)-
substituted compounds M(C6F5)4 (M = Si to Pb). Increasing the radius rM from M = Si to M = Pb
19
does not significantly simplify the F NMR spectra. Broad signals are observed indicating the
6
presence of inter-annular JFF couplings between ortho-fluorines.
207
The case of Pb(C6F5)4 is of particular interest since Pb is spin active with I = 1/2 and hence the
207
Pb spectrum of Pb(C6F5)4 was monitored revealing a deceptively simple pattern. It is not
207
necessary to simulate the Pb spectrum as the A part of the complex A[[MR]2X]4 case.
207
It is sufficient to approximate the experimental Pb NMR spectrum by the A part of
AM8R8X4 simulations:
H146197_00_01
802
-384 -388 -392 -396

(ppm)
207
Figure 607 : Pb NMR spectrum of Pb(C6F5)4. A part of AM8R8X4.
NMR Data for Pb(C6F5)4
δi Type [ppm]
1 A -391
2 M8 -121.4
3 R8 -157.5
4 X4 -147.5
νi [Hz]
1 A -32621.8338
2 M8 -45683.8053
3 R8 -59268.4906
4 X4 -55505.4095
Jik [Hz]
12 JAM 111.2000
13 JAR 45.9000
14 JAX 17.1000
HWB [Hz]
1 A 4
Coupling constants J23 = JMR, J24 = JMX, J34 = JRX do not influence the appearance of the A
spectrum, hence are set to 0 Hz for AM8R8X4 calculations. HWB tentatively set to 4 Hz.
H146197_00_01
803
For details read: "Tetrakis(pentafluorophenyl)lead(IV): crystal structure, semi empirical PM3

calculations and NMR studies". T. M. Klapöthke, B. Krumm, M. Niemitz, K. Polborn, C. M.
Rienäcker; J. Fluor. Chem. 104, 129-133 (2000).
Some Final Observations for C6F5 Compounds
If the inter-annular F-F distances in suitable model structures of type R(C6F5)4 are sufficiently
expanded, then a simplified spectral situation is expected approximating the parent [AC]2B
spectrum of C6F5 compounds. This situation is found for tetrakis(penta-fluorophenyl)-porphyrin,
abbreviated as LH2 below:
Tetrakis(pentafluorophenyl)-porphyrin as Ligand LH2 and Two Iron Complexes
F F F
F F F F F F
F F F F F F
H H H H H H
H H H H H H
F F N N F F F F N N F F F F N N F F
H
F NC Fe CN F F F F Fe Cl F
H
F F N N F F F F N N F F F F N N F F
H H H H H H
H H H H H H
F F F F F F
F F F F F F
F F F
- -
[LFe(III)(CN)2] (Low Spin) Ligand LH2 [LFe(II)Cl] (High Spin)
The total molecule of LH2 is not coplanar, but propeller shaped having S4 symmetry in the solid
state. Indeed the free ligand LH2 exhibits the [AC]2B spectral pattern of a simple C6F5 compound
with chemical shifts given below.
-
And this is true as well for [LFe(CN)2] , the anion of a diamagnetic low spin complex, but some line
broadening obscures the fine structure of this [AC]2B case. A strong additional increase of line
-
width and considerable contact shift contributions are monitored for the anion [LFeCl] of the
paramagnetic high spin complex. In addition the broad resonances of the ortho and the meta-
fluorines are split into pairs of distinct signals while the para signal appears as one singlet only.
This splitting is solvent dependent. No fine structure is resolved. Hence information on coupling
constants is lost.
H146197_00_01
804
19
282.3 MHz F NMR Data of Tetrakis(pentafluorophenyl)-porphyrin
and Some Selected Complexes. 5 mM Solution. 25°C. Int. ref. CFCl3.
Compound δF (ortho) δF (meta) δF (para) Solvent
Ligand LH2 -137.3 -162.1 -152.2 CD2Cl2

-
[LFe(III)(CN)2] Low Spin -137.6 -163.6 -153.2 CD2Cl2
[LFe(II)] intermediate -135.5 -161.4 -152.2 C6D5CD3

S=1
[LFe(II)(THF)2] High Spin -140.4 -165.3 -157.7 THF-d8

-
[LFe(II)F] High Spin -128.2 -160.9 -154.1 CD2Cl2
S=2 -130.2 -162.5
-
[LFe(II)Cl] High Spin -131.0 -165.1 -157.9 C6D5CD3
-132.2 -166.0
[LFe(III)Cl] High Spin -102.0 -152.1 -147.2 C6D5CD3

-105.1 -154.6
1
Note low field shift by paramagnetism - H NMR chemical shifts of the pyrrole protons:
a) of [LFe(II)Cl] , (tol-d8, 25°C) singlet at δH = 40.7 ppm,

-
b) of [LFe(III)(CN)2] , (CD2Cl2, 25°C) singlet at δH = 8.9 ppm.

-
For details on chemistry, NMR, paramagnetic compounds, and contact shift read:
B. Song, B: Park, C. Han; Bull. Korean Chem. Soc. 23, 119-122 (2002).
B. Song, B.-S. Yu; Bull. Korean Chem. Soc. 24, 981-985 (2003).
[LFe(III)Cl] reacts with CH3ONa to yield [LFe(III)OCH3]. Chemical shifts (solution in CDCl3): pyrrole
protons: singlet at δH = 81 ppm, methoxide protons: 4.9 ppm.
Read:
A. Stephenson, A. T. Bell; Inorg. Chem. 45, 5591-5599 (2006).
A. Stephenson, A. T. Bell; J. Amer. Chem. Soc. 127, 8635-8643 (2005).
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Disturbing the Symmetry of C6F5 Groups in C6F5SF3

F 7 6 6 F F
F 6
S S
F 6 7 F
F F 5 1 5 1 F F
F F 4 2 4 2 F F
F 3 3 F
19
The low temperature F NMR spectrum of pentafluorophenyltrifluorosulfurane reveals a loss of
symmetry which is indicated by δ1 ≠ δ5 and δ2 ≠ δ4. The pairs of ortho- and meta- fluorines in the
pentafluorophenyl group are no longer chemically equivalent, they are anisochronous under low
temperatures. Hence the skeleton of C6F5 gives rise to an ABCDE type system.
For details read: P. Meakin, D. W. Ovenall, W. A. Sheppard and J. P. Hesson; J. Amer. Chem.
Soc. 97, 522-528 (1975).
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Six Spins in C6H6-nFn
21 Six Spins in C6H6-nFn
6-Spin Cases - from C6H6 to C6F6 - 13 Compounds of Type C6H6-nFn (n = 0 to 6)
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Reports on this series of compounds and NMR investigations contain a multitude of didactically
1 19
useful information concerning H and F NMR techniques, symmetry and chemical equivalence. It
is beyond the scope of this manuscript to handle details of all those interesting spin systems. As a
substitute basic references are listed for deeper studies - in case you need that.
Selected References for NMR Studies on C6H6-nFn (n = 0 to 6)
C6H6-nFn C6H6-nFn
n Spin system Ref. n Spin system Ref.
0 A6 1 6 X6 1, 14, 20
1 [AB]2CX 1, 2, 8, 9, 15, 16 5 A[XY]2Z 1, 20
2a [ABX]2 1, 3, 6, 7, 16 4a [AXY]2 1, 11, 18
2b A[BX]2C 1,6, 10, 16, 19 4b [AX]2YZ 1, 12, 20
2c [[A]2X]2 1,6, 16 4c [A[X]2]2 1, 17, 18
3a [AX]2BY 1, 4
3b ABCXYZ 1,16, 21, 22
3c [AX]3 1, 5, 13
Cases 0 and 6 correspond to trivial singlet spectra. Case 3b will approximate AHMPRX at elevated
fields and hence is simple for direct analysis. Using the principles of sub-spectral analysis, if
necessary supported by measurements at elevated fields, readers should be able to tackle
successfully cases 1, 5, 2b, 4b, and 3a.
High lights in this series are symmetrical compounds 2a [ABX]2, 4a [AXY]2, 2c [[A]2X]2, 4c
[A[X]2]2, and 3c [AX]3 . It is useful and interesting to study details of those cases which are
described in the open literature as listed below (refs. 1, 5, 6, 13, 17, 18).
Remark: Use symmetry for simulations with TopSpin / DAISY.
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Starting Values for Your Own Simulations and Iterative Calculations
Coupling Constants [Hz] Observed for C6H6-nFn (n = 0 to 6)

3 4 5
Coupling J(ortho) J(meta) J(para)
n
JHH +7.453 to +9.950 +0.871 to +3.244 +0.255 to +0.653
n
JFH +7.540 to +10.846 +3.310 to +8.149 -2.698 to +0.348
n
JFF -20.821 to -18.487 -3.003 to +6.515 +3.869 to +17.646
Some Relevant References for NMR Studies of C6H6-nFn (n = 0 to 6)
1 V. Wray; L. Ernst, E. Lustig; J. Magn. Res. 27, 1-21 (1977).

2 E. Lustig, W. B. Monitz, P. Diehl, B. Bodmer; J. Chem. Phys. 49, 4550-4555 (1968).
3 L. Ernst, D. N. Lincoln, V. Wray; J. Magn. Res. 21, 115-128 (1976).
4 L. Ernst, V. Wray; J. Magn. Res. 28, 373-375 (1977).
5 V. Wray, D. N. Lincoln; J. Magn. Res. 18, 374-382 (1975). (This paper provides an extended
list of references for NMR studies on C6H6-nFn (n = 0 to 6).
6 I. Alkorta, F. Blanco, J. E. Del Bene, J. Elguero, L. Hernandez-Folgado, M. L. Jimeno; Magn.
Res. Chem. 48, 68-73 (2010)
7 R. Laatikainen, M. Niemitz, U. Weber, J. Sundelin, T. Hassinen, J. Vepsäläinen; J. Magn. Res.
120, 1 - 10 (1996).
8 R. R. Dean, W. McFarlane; J. Chem. Soc. (B), 1969, 509-512.
9 L. J. Lawrenson; J. Chem. Soc. 1965, 1117-1120.
10 R. J. Abraham, D. B. Macdonal, E. S. Pepper; J. Chem. Soc. (B) 1967, 835-841.
11 C. Barbier, H. Faucher, D. Gagnaire, A. Rousseau; J. Chim. Phys. 63, 283 (1966).
12 E. Lustig, P. Diehl; J. Chem. Phys. 44, 2974-2978 (1966).
13 R. G. Jones, R. C. Hirst, H. J. Bernstein; Can. J. Chem. 43, 683 (1965)
14 L. C. Snyder, E. W. Anderson; J. Chem. Phys. 42, 3336-3337 (1965).
15 T. E. Page, Jr.; Mol. Phys. 13, 523-532 (1967).
16 J. E. Loemker, K. M. Pryse, J. M. Read, Jr., J. H. Goldstein; Can. J. Chem. 47, 209-213
(1969).
17 J. E. Loemker, J. M. Read, Jr., J. H. Goldstein; J. Mol. Spect. 5, 284-293 (1969).
18 J. Gerritsen, G. Koopmans, H. S. Rollema, C. McLean; J. Magn. Res. 8, 20-34 (1972).
19 G. J. den Otter, J. Gerritsen, C. McLean; J. Mol. Struct. 16, 379-387 (1972).
20 G. J. den Otter, C. McLean; J. Mol. Struct. 31, 47-56 (1972).
21 R. J. Abraham, M. A. Cooper; Chem. Comm. 1968, 1285-1286.
22 E. Lustig, E. Hansen, P. Diehl, H. Kellerhals; J. Chem. Phys. 51, 1839-1845 (1969).
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Seven Spins: Quinolines
22 Seven Spins: Quinolines
Comparing 19F and 1H and NMR Spectra of C9NF7, C9NH7, C9ONH7
19
7 single spins in Perfluoroquinoline C9NF7 give rise to a first order F NMR spectrum even at
1
lower fields. Quinoline C9NH7 yields a second order H NMR spectrum which simplifies at higher
fields. Compare spectra and data shown below:
F F 4 3 H H
F F 5 2 H H
F N F 6 N 1 H N H
F 7 H
19
Figure 608 : Simulated 84.7 MHz F NMR spectrum of perfluoroquinoline C9NF7
1
Figure 609 : Simulated 500 MHz H NMR spectrum of quinoline C9NH7
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811
Original NMR Data for Quinoline and Perfluoroquinoline

Parameter Perfluoroquinoline Type Quinoline Type
19 1
84.7 MHz F NMR 100 MHz H NMR
C9NF7 C9NH7
δi
)
*
1 -73.98 A 8.8024 A
2 -161.93 G 7.2232 G
3 -125.73 B 7.9612 C
4 -147,06 C 7.6577 D
5 -156.25 F 7.4052 F
6 -152.60 E 7.5910 E
7 -149.77 D 8.0682 B
νi
1 -6263.8348 A 880.24 G
2 -13710.4997 G 722.32 A
3 -10645.4711 B 796.12 F
4 -12451.4673 C 765.77 E
5 -13229.5781 F 740.52 B
6 -12920.5352 E 759.10 C
7 -12680.9211 D 806.82 D
Jik
12 -27.70 4.18
13 26.50 1.78
14 -3.10 -0.11
15 8.30 0.29
16 -1.50 0.06
17 6.10 0.27
23 -14.50 8.24
24 7.00 0.24
25 -2.50 0.13
26 8.15 0.30
27 -4.04 -0.13
34 48.00 -0.37
35 4.55 0.19
36 -3.40 -0.14
37 1.50 0.85
45 -17.90 8.20
46 1.90 1.44
47 14.95 0.67
56 -19.15 6.92
57 2.45 1.23
67 -17.10 8.53
Parameters: Red: pyridine ring. Blue: benzene ring. Green: inter-annular couplings.
)
* Referenced vs. CFCl3. Note: Signs of chemical shifts and resonance frequencies were adjusted
to IUPAC definition.
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22.1 Simple 7-Spin Homonuclear First Order System in

Perfluoroquinoline C9NF7
19
The F NMR spectrum of Perfluoroquinoline C9NF7 is of first order character, even at frequencies
as low as 84.7 MHz. Since all 21 coupling constants are larger than the spectral half width,
multiplets are observed for each of those 7 fluorine nuclei yielding a total of 448 lines. Note the
4
remarkably large peri-coupling J34 and the magnitude and sign of all the other inter-annular
n n
couplings JFF. For even n the sign of inter-annular couplings JFF is negative, for uneven n
positive.
19
Expansions for an 84.7 MHz F NMR Spectrum of Perfluoroquinoline C9NF7:
-6220 -6240 -6260 -6280 -6300 -6320

(Hz)
Figure 610 : A - F1
-10590 -10620 -10650 -10680

(Hz)
Figure 611 : B - F3
-12420 -12450 -12480

(Hz)
Figure 612 : C - F4
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-12630 -12660 -12690 -12720

(Hz)
Figure 613 : D - F7
-12870 -12900 -12930 -12960

(Hz)
Figure 614 : E - F6
-13200 -13230 -13260

(Hz)
Figure 615 : F - F5
-13680 -13710 -13740

(Hz)
Figure 616 : G - F2
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Hence, in principle, the spectrum of perfluoroquinoline C9NF7 is simple - but laborious to analyze
manually. TopSpin / DAISY tools, e. g. Multiplet Analysis, will help.
Data for perfluoroquinoline C9NF7 and related derivatives of fluorinated quinoline are described in
1)
. For fluorine chemists it might be interesting to compare corresponding NMR data for
2) 3)
perfluoroisoquinoline and perfluoroquinazoline .
Read:
a) R. S. Matthews; Org. Magn. Res. 8, 240-245 (1976).
b) R. S. Matthews; Org. Magn. Res. 8, 628-631 (1976).
c) R. S. Matthews; Org. Magn. Res. 9, 318-321 (1977).
22.2 Complex 7-Spin Homonuclear Second Order System in

Quinoline C9NH7
1
The H NMR spectrum of quinoline C9NH7 is of complex second order character for frequencies
lower than 300 MHz. At and above 300 MHz resonances for all 7 protons will be neatly separated.
n
Most of the inter-annular couplings JHH are small, below the spectral half width commonly
observed at high field spectrometers and hence will be overlooked by routine NMR. M. Antimonelli
1
and O. Sciavovelli performed a fine 100 MHz H NMR study on quinoline C9NH7 and determined
the inter-annular couplings by INDOR technique. Numerical results for corresponding NMR
parameters are listed in the previous chapter.
For details on quinoline and derivatives read:

a) M. Antimonelli and O. Sciavovelli, Org. Magn. Res. 12, 17-23 (1979).
b) G. Barbieri, R. Benassi, P. Lazzaretti, L. Schenetti, F. Taddei; Org. Magn. Res. 7, 451-454
(1975).
1
Exercise: Simulate H NMR spectra of quinoline C9NH7 and study the expected spectral
appearance using spectrometers between 100 MHz and 500 MHz.
Comments: Inter-annular couplings may be overlooked.
1
B. C. Baker and D. T. Sawyer characterized 8-quinolinol and corresponding ions by H NMR.
H146197_00_01
815
H4 H3 H4 H3 H4 H3
H5 H2 H5 H2 H5 H2
H6 N H1 H6 N H1 H6 N+ H1
O- OH OH H
[Ox]- HOx [H2Ox]+
Solutions in DMSO were measured at 100 MHz. The authors did not detect inter-annular couplings.
As we know now, those long range couplings are smaller than the half width at half height of the
lines in such samples.
Simulated 500 MHz NMR spectra are shown below:
6.5 6.0 5.5 5.0 4.5 4.0
6.8 6.4 6.0 5.6 5.2 4.8 4.4
6.5 6.0 5.5 5.0 4.5 4.0

(ppm)
1 - +
Figure 617 : Simulated 500 MHz H NMR spectra. Upper: [Ox] . Middle: HOx . Lower: [H2Ox] .
H146197_00_01
816
1 - +
H NMR Data of Species [Ox] , HOx , and [H2Ox]
- - + +
Parameter [Ox] [Ox] HOx HOx [H2Ox] [H2Ox]
δi
1 5.903 A 6.268 A 6.527 B
2 4.674 C 4.945 C 5.531 C
3 5.434 B 5.714 B 6.594 A
4 3.993 E 4.816 E 5.154 D
5 4.605 D 4.872 D 5.149 E
6 3.985 F 4.578 F 5.017 F
Jik
12 4.09 4.14 5.38
13 1.69 1.63 1.28
23 8.18 8.29 8.41
45 7.71 7.95 8.77
46 8.04 7.82 7.77
56 1.24 1.10 1.02
Inter-annular couplings Jik are given as zero for: 14, 15, 16, 24, 25, 26, 34, 35, and 36.
For details of the original 100 MHz study read:

B. C. Baker and D. T. Sawyer; Anal. Chem. 40, 1945-1951 (1968).
This paper also reports about:
1 -
H NMR studies of metal complexes ML2 (M = Mg, Zn, Sn, Pb, Hg, Pt; L = [Ox] ).
1 13
Results from a " H and C NMR study of 8-hydroxyquinoline and some of its 5-substitued
analogues" are reported by:
J. Kidric, D. Hadi, D. Kocjan and V. Rutar, Org. Magn. Res. 15, 280-284 (1981).
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Seven to Twelve Spins: Polycyclic Aromatic Ring Compounds
23 Seven to Twelve Spins: Polycyclic

Aromatic Ring Compounds
1
23.1 H NMR Spectrum of Naphthalene – an [AB]4 (D2h) System
– 8-Spin Case
A´´´ A H H 8 1
B´´´ B H H 7 2
B´´ B´ H H 6 3
A´´ A´ H H 5 3
1
Analysis of a 100 MHz NMR spectrum from naphthalene in CD3COCD3 reveals a very complex
[AB]4 (D2h) system.
1
H NMR Data from Naphthalene C10H8
Parameter Data
δi [ppm]
1, 4, 5, 8 H 7.8540
2, 3, 6, 7 H 7.4611
Jik [Hz]
3
12, 34, 56, 78 JHH 8.32
4
13, 24, 57, 68 JHH 1.24
5
14, 58 JHH 0.75
5
15, 48 JHH 0.85
6
16, 25 JHH 0.22
5
17, 28 JHH -0.14
4
18, 45 JHH -0.47
3
23, 67 JHH 6.84
7
26, 37 JHH 0.28
6
27, 36 JHH 0.12
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819
An [AB]4 simulation shows the overlap of 1502 lines. If we neglect the inter-annular couplings from
naphthalene, then a more simple [AB]2 case is simulated as shown below. This [AB]4 is clearly a
case for automated analysis. Manual analysis of the [AB]4 case does not yield more than a guess
for N = JAB + JAB´ + JAB´´ + JAB´´´ as indicated in red below.
7.90 7.80 7.70 7.60 7.50 7.40

(ppm)
Figure 618 : [AB]4 - simulation including inter-annular couplings.
7.90 7.80 7.70 7.60 7.50 7.40

(ppm)
Figure 619 : [AB]2 - simulation - excluding long range inter-annular couplings
Data from: L. Cassidei, O. Sciacovelli; Org. Magn. Res. 15, 257-262 (1981).
Compare an earlier paper on naphthalene: R. W. Crecely, J. H. Goldstein; Org. Magn. Res. 2, 613-
618 (1970).
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23.2 1
H NMR Parameters of α-and β-Naphthyl Compounds
C8H7R – 7-Spin Cases
H R H H
H H H R
H H H H
H H H H
H NMR Parameters of α-and β-Naphthyl Compounds C8H7R

1
Parameter Type 1-NMe2 1-NO2 2-NMe2 2-NO2

δ1 δH - - 6.769 8.650
δ2 δH 6.933 8.105 - -
δ3 δH 7.240 7.447 6.991 8.138
δ4 δH 7.377 7.993 7.543 7.845
δ5 δH 7.767 7.842 7.545 7.849
δ6 δH 7.323 7.526 7.086 7.601
δ7 δH 7.355 7.616 7.237 7.555
δ8 δH 8.139 8.489 7.508 7.927
4
J13 JHH - - 2.5 2.35
5
J14 JHH - - 0.55 0.55
3
J23 JHH 7.45 7.65 - -
4
J24 JHH 1.1 1.25 - -
3
J34 JHH 8.3 8.25 9.1 8.95
3
J56 JHH 8.2 8.35 8.1 8.2
4
J57 JHH 1.45 1.2 1.3 1.2
5
J58 JHH 0.6 0.75 0.7 0.7
3
J67 JHH 6.9 6.85 6.8 6.9
4
J68 JHH 1.5 1.15 1.1 1.3
3
J78 JHH 8.3 8.85 8.5 8.1
1
H NMR data obtained from 100 MHz studies on 0.48 M solutions in CCl4. 27°C.
Remarks: Jik data not given in the table above were not observed and are assumed to be zero. No
attempts to determine inter-annular-couplings were made.
Read: V. Lucchini, P. R. Wells; Org. Magn. Res. 8, 137-140 (1976).
H146197_00_01
821
1
23.3 H NMR Spectrum of Anthracene – 10-Spin Case
H H H 9 10 1
H H 8 2
H H 7 3
H H H 6 5 4
Formally an [[AB]2X]2 might be expected. But the inter-annular couplings are very small (or not
1
resolved). Hence a total H NMR spectrum appears simply as the overlay of an [AB]2 (8 protons)
and an X2 (2 protons) part. But the A- and the X-lines are broader than the B-lines indicating weak
4 5
couplings J1,10 = JHH(peri) or more likely J15 = JHH.
This case was discussed in the early days of NMR.

Read: N. Jonathan, S. Gordon, B. P. Dailey; J. Chem. Phys. 36, 2443 (1962).
1
23.4 H NMR Spectrum of Thioxanthene Carbanion
– 9-Spin Case
Considerable upfield shifts were observed for chemical shifts δH of carbanions from
9,10-dihydroanthracene, Xanthene, and Thioxanthene.
H H H 8 9 1
H H 7 2
- -
H X H 6 X 3
H H 5 4
X = CH2, O, S.
Within this context paramagnetic ring current effects (Paratropism) were discussed.
If X = S, in the thioxanthene anion, an [ABCD]2X spectrum is expected. But inter-annular couplings

are negligible and hence at first sight patterns resemble an overlay of ABCD (8 protons) and
H146197_00_01
822
X1 (1 proton). Only one long range coupling was extracted from the small splitting of H4 (C) and H9
4
(X) signals: J49 = J59 = JHH(peri) = 0.8 Hz.
Parameters Type Data

δ1 = δ8 δH D 5.54 [ppm]
δ2 = δ7 δH B 6.21 [ppm]
δ3= δ6 δH A 6.68 [ppm]
δ4 = δ5 δH C 5.94 [ppm]
δ9 δH X 3.93 [ppm]
3
J12 = J78 JHH BD 7.8 [Hz]
4
J13 = J68 JHH AD 1.4 [Hz]
5
J14 = J58 JHH CD 0.3 [Hz]
3
J23 = J67 JHH AB 7.1 [Hz]
4
J24 = J57 JHH BC 1.4 [Hz]
3
J34 = J56 JHH AC 7.2 [Hz]
5
J49 = J59 JHH CX 0.7 [Hz]
Data from: H. W. Vos, Y. W. Baker, C. McLean, N. H. Velthorst; Org. Magn. Res. 6, 245-249
(1974).
1
23.5 H NMR Spectrum of Phenanthrene – 10-Spin Case
H H
H H
H H
H H H H
An [ABCDX]2 is expected, but, since inter-annular couplings are zero or not resolved, in practice
two separate systems are observed and discussed: one ABCD (2x4 H) and one X 2 (2 H).
H146197_00_01
823
1
A substantial paper on H NMR of phenanthrene and some methyl substituted derivatives of
phenanthrene was presented by Bartle et al.:
H H H H H H H H H 3C H
H CH3 H H H H H H H H
H H H CH3 H H H H H H
H H H H H H H H H H H CH3 H H CH3 H H H H H
1 2 3 4 9
ABC+MNOP+XY ABC+MNOP+XY
ABC+MNOP+XY ABC+MNOP+XY ABCD+MNOP+X
ABM+NOPR+XY ABM+NOPR+XY
H H H H H H H H H 3C CH3
H 3C CH3 H H H H H H H H
H H H 3C CH3 H H H H H H
H H H H H H H H H 3C H H CH3 H H 3C CH3 H H H H H
1,8 2,7 3,6 4,5 9,10

[ABC]2+X2 [ABC]2+X2 [ABC]2+X2 [ABC]2+X2 [ABCD]2
ABC+X2 ABC+X2 ABC+X2 ABC+X2 ABCD
Read: K. D. Bartle, J. A. Smith; Spectr. Chem. Acta 23A, 1689-1714 (1967).
In a second paper Bartle et al. published results from detailed studies on mono substituted
phenanthrenes:
R H
H H
R = F, Cl, Br, I, CN
H H
H H H H
and further disubstituted phenanthrenes.
Read: K. D. Bartels, J. A. Smith; Spectrochimica Acta 23A, 1715-1734 (1967).

A shorter report on mono substituted phenanthrenes was given by C. Balo, F. Fernandez, C.
Gonzalez, C. Lopez; Spectrochimica 50A, 937-940 (1994).
These papers will help you to solve NMR spectra from phenanthrene derivatives.
H146197_00_01
824
1
23.6 H NMR Spectrum of 3,4-Dibenzoperylene
– 12 Spin System Fragmented
H H 1 10
H H 2 9
H 1´
H 2´
H 8
H H 3´ 7
H H H 4´ 5 6
1
Corresponding H NMR spectra are simple to calculate by using the fragmentation technique from
TopSpin / DAISY as shown in the following table:
Fragment 1 Fragment 1 Type H1 and H2

δH 1 B 8.240 [ppm]
2 A 8.980 [ppm]
Jik 12 9.1 [Hz]
Fragment 2 Fragment 2 H1´ to H4´
δH 1 A 8.975 [ppm]
2 C 7.740 [ppm]
3 D 7.685 [ppm]
4 B 8.190 [ppm]
Jik 12 8.6 [Hz]
13 1.2 [Hz]
14 0.6 [Hz]
23 6.8 [Hz]
24 1.2 [Hz]
34 8.1 [Hz]
Fragment 3 Fragment 3 H5
δH 1 A 8.415 [ppm]
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Fragment 4 Fragment 4 H6 and H7

δH 1 A 7.910 [ppm]
2 B 7.840 [ppm]
Jik 12 9.0 [Hz]
Fragment 5 Fragment 5 H8 to H10
δH 1 B 7.990 [ppm]
2 C 7.885 [ppm]
3 A 8.135 [ppm]
Jik 12 7.4 [Hz]
13 1.0 [Hz]
23 7.7 [Hz]
If the concept of fragmentation is justified (no couplings exist between the fragments) then this 12
spin problem ends up simply as a superposition of five individual spectra: one A1, two AB, one
ABC, and one ABCD type.
Exercise: Simulate 500 MHz spectra A1, AX, AMX, AMXY, AMRX approximations.
Simulations
9.0 8.8 8.6 8.4 8.2 8.0 7.8

(ppm)
1
Figure 620 : Total 200 MHz H NMR spectrum of 3,4-Dibenzoperylene
H146197_00_01
826
9.0 8.8 8.6 8.4 8.2 8.0 7.8

(ppm)
Figure 621 : Fragment 1
9.0 8.8 8.6 8.4 8.2 8.0 7.8

(ppm)
9.0 8.8 8.6 8.4 8.2 8.0 7.8

(ppm)
H146197_00_01
827
9.0 8.8 8.6 8.4 8.2 8.0 7.8

(ppm)
9.0 8.8 8.6 8.4 8.2 8.0 7.8

(ppm)
Exercise: Reanalyze the total spectrum using the list of transition frequencies and intensities
shown below.
H146197_00_01
828
1
Simulated 500 MHz H NMR Spectrum - Transition Frequencies and Intensities
4494.6122 0.9754 4207.5059 1.0000
4485.5122 1.0246
4124.4999 1.0246
4115.3999 0.9754
4512.8890 0.0015 3960.0748 0.7510
4492.7371 0.9828 3951.0748 1.2490
4492.1369 0.9857 3923.9362 1.2490
4491.3965 0.9852 3914.9362 0.7510
4490.8519 0.9890
4484.2778 1.0083 Fragment 5
4483.6219 1.0127 4071.9793 0.9270
4482.9372 1.0142 4070.9362 0.9504
4482.3369 1.0174 4064.3194 1.0444
4462.7853 0.0018 4063.2764 1.0778
4119.5736 0.0013 3999.4820 0.8560
4100.0226 0.9641 3998.4389 0.8638
4099.4223 0.9616 3992.0849 1.1725
4098.7370 0.9747 3991.0418 1.1078
4098.0811 0.9709 3949.6555 1.2169
4092.0074 1.0265 3942.2585 0.9053
4091.4627 1.0222 3941.9957 1.0632
4090.7218 1.0396 3934.5986 0.8143
4090.1215 1.0359
4069.9702 0.0019
3878.6872 0.7742
3877.4016 0.8187
3871.8882 1.2652
3870.6026 1.1973
3870.2278 0.6715
3868.8866 0.7466
3863.4289 1.3131
3862.0877 1.2146
3850.0759 1.2789
3848.7353 1.3496
3843.2769 0.7886
3842.0607 1.1597
3841.9364 0.7085
3840.7757 1.2007
3835.2617 0.7805
3833.9767 0.7321
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Practical Examples from Multi-Spin Systems with Symmetry
24 Practical Examples from Multi-

Spin Systems with Symmetry
A Chapter on Symmetric Spin Systems: the [AXn]2 System - "Harris-Multiplets"
1
24.1 H Spectrum of Tetramethyldiphosphinedisulphide
[(CH3)2P(S)]2 – X Part
25 20 15 10 5 0 -5 -10 -15 -20 -25

(Hz)
Figure 626 : H NMR spectrum of [(CH3)2P(S)]2. X part of [AX6]2 system. νH centered at 0 Hz.
1
1
The H NMR spectrum represents the X part of an [AXn]2 (n = 6) type system.
JXX´
JAX´
H 3C CH3
S P P S Xn A A ´ Xń
H 3C CH3
JAX JAA´
This spectral pattern is field independent and governed by four coupling constants JAX, JAX´, JAA´,
5
and JXX´. If JXX´ = 0, and this is true for JHH in the H3C-P-P-CH3 skeleton, then explicit algebraic
equations can be derived for transition frequencies and transition intensities. HARRIS discussed in
1
details the H NMR spectra (the X part) of such systems. Two linearly combined parameters are
important for spectral analysis N = JAX+JAX´ and L = JAX - JAX´. The N-lines are recognized as a
sharp doublet centered at νX contributing 50% of the total intensity observed in the X part. The
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Practical Examples from Multi-Spin-Systems with Symmetry
remaining 50% are given by so called χ-lines, consisting of n weighted sets of four-line sub-spectra
symmetrically placed in pairs around the resonance frequency νX (here νH). Those sets of χ-lines
appear similar to ab type sub-spectra, but close inspection reveals that only one set of those χ-lines
will have true ab-character for transitions intensities: for χ = 1. Each set of χ-lines (χ = 1 to n) will
appear as a pair of outer and a pair of inner lines each pair split by:
Frequencies
So ( χ) = χ 2L2 + J2AA´ + (χ − 1)2 L2 + J2AA´ Separation of outer lines
Si (χ) = χ2L2 + J2AA´ − (χ − 1)2 L2 + J2AA´ Separation of inner lines
1
ν1(χ) =ν X + So (χ) Outer line
2
1
ν 2 (χ) =ν X + Si (χ) Inner line
2
1
ν3 (χ) =ν X − Si (χ) Inner line
2
1
ν 4 (χ) =ν X − So (χ) Outer line
2
Intensities
n
1
Io (=
χ) (1− g) ∑ r nCr nCr −χ Intensity of outer lines
2n r= χ
n
1
Ii (=
χ) (1+ g) ∑ r nCr nCr −χ Intensity of inner lines
2n r= χ
χ (χ − 1)L2 + J2AA´
g= Weighting factor
[χ 2 L2 + J2AA´ ][(χ − 1)2 L2 + J2AA´ ]
Corresponding intensities decrease rapidly with increasing χ. It is sufficient to evaluate the strongest
set for χ = 1:
So (1) = L2 + J2AA´ + JAA´ Separation of outer lines
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Si (1) = L2 + J2AA´ − JAA´ Separation of inner lines
Hence
1
=
JAA´ (So (1) − Si (1))
2
=L So (1) ⋅ Si (1)
1
J=
AX (N + L)
2
1
J=
AX´ (N − L)
2
Note: The coupling constant JAA´ is directly accessible from the X spectrum!
This method described above is widely used to determine (the absolute value of) JPP in symmetric
organophosphorous and coordination compounds and in general for [AXn]2 systems.
For details of [AXn]2 read:

a) General Theory: R. K. Harris, Can. J. Chem. 42, 2275-2281 (1964);
b) Applications: R. K. Harris and R. G. Hayter; Can. J. Chem. 42, 2282-2291 (1964.
Note:
If IJAAI << ILI or IJAAI = 0, then a deceptively simple doublet is observed in the X part,
If IJAAI >> ILI or ILI = 0, then a deceptively simple triplet is observed in the X part, some times
called a "Harris-Triplet". This situation is found in tetramethyldiphosphine [(CH3)2P]2.
Read: E. G. Finer, R. K. Harris; Mol. Phys. 12, 457 (1967), ibid. 13, 65 (1967)
Remember: The N-lines will have smaller spectral half widths than corresponding χ-lines. Hence
standard simulation programs will not be able to simulate perfectly the spectral appearance of [AXn]2
systems when using a uniform line shape for all transitions.
2
For tetramethyldiphosphinedisulphide the following data were found: JAX = JPH = -12.74 Hz. JAX´ =
3 1
JPH = +7.26 Hz. JAA´ = JPP = 18.7 Hz. JXX´ = 0. In a simulation shown below the resonance
frequency νX = νH is centered arbitrarily at 0 Hz.
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1
H NMR Spectrum of Tetramethyldiphosphinedisulphide
-23.04
23.04
-2.74
-4.34
4.34
2.74
25 20 15 10 5 0 -5 -10 -15 -20 -25

(Hz)
Blue: N Lines. Red: Si(1) χ-lines. Green: So(1) χ-lines. Magenta: JAA´ = JPP.
Figure 627 : H NMR spectrum of [(CH3)2P(S)]2. X part of [AXn]2 system. νH centered at 0 Hz.
1
24.2 A Part of [AXn]2: The 31P NMR Spectrum of [(CH3O)2P(O)]2O
31
MOWTHORPE and CHAPMAN dealt with the P NMR spectra (the A part) of tetramethylesters of
pyrophosphoric and hypodiphosphoric acids:
JXX´
JAX´
H3CO OCH3 H3CO OCH3
[AXn]2 O P O P O O P P O Xn A A´ Xń
H3CO OCH3 H3CO OCH3

JAX JAA´
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3 5
The following parameters of tetramethylpyrophosphate were found: JAX = JPH = 11.6 Hz. JAX´ = JPH
= 0 Hz. JAA´ = JPP = 14.3 Hz. For the simulation shown below the resonance frequency νX = νP was
2
set arbitrarily to -1000 Hz.
-960 -980 -1000 -1020 -1040

(Hz)
31
Figure 628 : P NMR spectrum of tetramethylpyrophosphate
General Note for the A Part of [AXn]2 Systems
If IJAAI >> ILI then a deceptively simple multiplet of (2n+1) lines is observed in the A part of the
[AXn]2 system. Effectively we see the A part of a hypothetical A2X2n spectrum.
1
For completeness the corresponding H NMR spectrum of tetramethylpyrophosphate is shown
below using a resonance frequency νX = νH set to 0 Hz. Analyze this spectrum.
40 20 0 -20 -40
(Hz)
1
Figure 629 : H NMR spectrum of tetramethylpyrophosphate.
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For details of [AXn]2 read:

D. J. Mowthorpe, A. C. Chapman; Spectrochimica Acta 23A, 451-453 (1967)
The [AXn]2 system is widely spread in practical examples from inorganic chemistry, e. g.
-
in anions of hepta-coordinated uranium complexes like [UO2[S2PR2]2Cl] (R=CH3, CH3O).
Read: A. A. Pinkerton, D. L. Pisaniello, F. Zonneville; Inorg. Chem. 82, 153-156 (1984).
Further examples are found in many metal complexes holding ligands PH3 and PF3, e.g. cis-
4
[Cr(CO)4(PH3)2], cis-[W(CO)4(PH3)2], cis-[Mo(CO)4(PF3)2], etc., where long range couplings JHH and
4
JFF are zero.
Read:
a) E. O. Fischer et al.; J. Org. Met. Chem. 14, P9-P12 (1968), ibid. 15, 157-163 (1968), ibid. 19,
377-385 (1969).
b) M. Scheer et al.; Organometallics 29, 5187-5191 (2010).
c) C. G. Barlow, J. F. Nixon, J. R. Swain; J. Chem. Soc. (A) 1969, 1082.
Exercise: Study some examples from organic chemistry, e. g. meso and d,l forms of 2,3-
dibromobutane CH3-CHBr-CHBr-CH3 and the cyclic carbonates of meso and d,l 2,3-butanediols.
Read: F. A. L. Anet; J. Amer. Chem. Soc. 84, 747-752 (1962).
1
Simulate the H NMR spectra from cyclic carbonates of meso- and d,l-2,3-butanediols. Data are
listed below.
H CH3
O O
H H
C O C O
CH3 H
O O
CH3 CH3
meso d,l
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NMR Data for Cyclic Carbonates of Meso and d,l 2,3-Butanediols
Parameter Type meso d,l

δH(CH3) δ(X3) 1.374 1.413 [ppm]
δH(H) δ(A) 5.840 5.660 [ppm]

3
JHH JAX 6.55 6.10 [Hz]
4
JHH JAX´ -0.15 -0.10 [Hz]
3
JHH JAA´ 7.35 7.20 [Hz]
5
JHH JXX´ 0 0 [Hz]
Note: Equations derived for A and X parts of [AXn]2 spectra are valid only if ν A − ν X >> L . If
νA − νX decreases towards L than [ABn]2 case are observed. This situation is true for cis- and
trans-CH3-CH=CH=CH3 at lower fields.
Remember: Equations derived for the A and the X parts of [AXn]2 spectra are NOT valid if JXX´ ≠ 0 .
19 31
E. g.: Those conditions are fulfilled for the F and the P NMR spectra in the linear cation of the
19 1 31 1
gold(I) complex [Au(PF3)2][Sb2F11] and the proton decoupled F{ H} and P{ H} NMR spectra of
N,N´-dimethyl-1,3,2,4-diazadiphosphetidine [CH3N-PF3]2:
CH3
F3 P PF3
CH3
Read: B. Bley, M. Bodenbinder, G. Balzer, H. Willner, H. Hägele, F. Mistry, F. Aubke; Can. J. Chem.
74, 2392-2394 (1996). For the diazadiphosphetidine case read the pioneering paper of R. K. Harris,
C. Woodmann; Mol. Phys. 10, 437 (1967).
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24.3 Expansions to More Complex Problems:
MANN et al. synthesised coordination compounds involving the ligand t-Bu2PH, e.g. [trans-PdCl2(t-
1
Bu2PH)2] and analyzed the M- and X parts of the corresponding [AMX18]2 system by H NMR
spectroscopy.
For details read:
a) B. E. Mann; J. Chem. Soc. (A) 1970, 3050.
b) A. Bright, B. E. Mann, C. Masters, B. L. Shaw, K, M. Slade, R. E. Stainbank; J. Chem. Soc (A)
1971, 1826.
Compounds like [Me(t-Bu)P]2, [Me(t-Bu)P(S)]2, [Me(t-Bu)P(S)]2O, or Me2Pt(P(OMe)3)2 (Me = CH3,

tBu = C(CH3)3) gave rise to [AM3X9]2 spectra. Algebraic expressions for transitions frequencies and
1 31
intensities were derived. H and P NMR spectra were analyzed and simulated successfully.
1
100 MHz H NMR Spectrum of [Me(t-Bu)P(S)]2 in C6D6. [AM3X9]2 Case.
1
Figure 630 : 100 MHz H NMR spectrum of [Me(t-Bu)P(S)]2 in C6D6. [AM3X9]2 case.
Upper: experimental. Lower: simulated. Left: Methyl group. δH = 1.67 ppm. JPH = -11.94 Hz. JPH =
2 3
+7.39 Hz. Right: t-Butyl group. δH = 1.32 ppm. JPH = +18.30 Hz. JPH = 0 Hz. JPP = 118.05 Hz. Line
3 5 1
width: N-lines 0.6 Hz. χ-Lines 1.2 Hz. (δP = 48.05 ppm).
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Read:
a) G. Hägele, R. K. Harris, J. M. Nichols; J. Chem. Soc. Dalton Trans. 1973, 79.
b) G. Hägele, J. Lorberth; Org. Magn. Res. 9, 325 (1977).
Finally a general expansion to [A ∑ Xni ]2 systems was derived. Those complex systems are
i
i
beyond the scope of this manuscript.
If you want to learn more about the background theory then read:
a) The X parts: G. Hägele und R. K. Harris; Ber. d. Bunsenges. 76, 910 (1972).
b) The A part: G. Hägele; Ber. d. Bunsenges. 78, 43 (1974).
Some Remarks
H SCH3 F F F P(O)(OR)2
C C C C
H SCH3 (RO)2(O)P P(O)(OR)2 (RO)2(O)P F
R = CH(CH3)2, CH2CH3.
2
1,4-Difluoro-2,3-bis(methylmercapto)benzene gives rise to [AM3X]2 spectra. But neither JAA = JHH)
5
nor JXX = JFF are zero! Hence this system can not be dealt with using equations valid for [Me(t-
Bu)P(S)]2.
See above and read: G. Hägele, J. Richter, M. Peach; Org. Magn. Res. 6, 374-379 (1974).
19 1 31 1
F{ H} and P{ H} NMR spectra of cis- and trans-1,2-difluoro-ethylene-1,2-bisphosphonic acid
19 31
tetraalkylesters reveal the typical spectral pattern of [AM]2 systems. The undisturbed F and P
NMR spectra are more complex and described by [AMXn]2 systems where the long range coupling
JXX´ = JHH = 0 but JAA´ = JPP ≠ 0 and JMM´ = JFF ≠ 0.
7 3 3
Methylesters P(O)(OCH3)2 correspond to straight [AMX6]2 systems. Simplifications are justified for
4
ethyl and isopropylesters P(O)(OCH2CH3)2 and P(O)(OCH(CH3)2)2. If JPH = JPOCCH3 is zero or
19 31
negligibly small, then the F and P NMR spectra may be described by [AMX2]2 or [AMX4]2 resp..
19 31
Simulate F and P NMR spectra using the example of trans-1,2-difluoro-ethylene-1,2-
bisphosphonic acid tetraisopropylester and understand more of those systems.
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NMR Data of Trans-((CH3)2CHO)2(O)P-CF=FC-P(O)(OCH(CH3)2)2
Parameter Type Data

δA δP -1.403 [ppm]
δM δF 11.772 [ppm]
δX δH 4.64 [ppm]
2
JAM JPF 88.25 [Hz]
3
JAM´ JPF -6,25 [Hz]
3
JAX JPH 6.2 [Hz]
6
JAX´ JPH 0 [Hz]
5
JMX JFH 0 [Hz]
6
JMX´ JFH 0 [Hz]
3
JAA´ JPP 33.4 [Hz]
3
JMM´ JFF -146.3 [Hz]
9
JXX´ JHH 0 [Hz]
50 vol % in mixture of solvents and references: CCl4/C6D6/C6D6/TMS, 50/40/5/5 % v/v.

Data from: R. Dittrich, G. Hägele; Phosphorus and Sulfur 10, 127-132 (1981).
3 3
Vary parameters JPP and JPH and study changes in the spectral pattern. Then read the paper by L.
G. Sprague, D. J. Burton, R. D. Guneratne, W. E. Bennett; J. Fluorine Chem. 49, 75-85 (1990),
where synthesis and NMR data of cis- and trans-1,2-difluoro-ethylene-1,2-bisphosphonic acid
tetraethylesters are described. What do you think? Is this spectral analysis correct?
24.4 The [AXn]3 System: Molecules with Threefold Symmetry
Mesitylene 1,3,5-C6H3(CH3)3, perfluoromesitylene 1,3,5-C6F3(CF3)3, 1,3,5-tris-

trifluoromethylbenzene 1,3,5-C6H3(CF3)3, tris-substituted cyclophosphazatriene cis-N3P3Cl3(OCH3)3
or the molybdenum complex fac-[Mo(CO)3(PF3)3] and fac-[Cr(CO)3(PH3)3] give rise to [AX3]3 spectra.
1,3,5-trifluoro-2,4,6-tris(trimethylsilyl)benzene C6F3[Si(CH3)3]3 yields [AX9]3 spectra, while
N3P3(N(CH3)2)6 represents an [AX12]3 case.
For special situations of the general case [AXn]3, where JXX = 0, explicit algebraic expressions for
transition frequencies and transition intensities were derived. If you want to learn more about
background theory then read the paper by E. G. Finer and R. K. Harris, J. Chem. Soc (A) 1969,
1972-1967. NMR spectra of fac-[Mo(CO)3(PF3)3] are described in R. K. Harris, R. Schmutzler, J. R.
Woplin; Ber. Bunsenges. Phys. Chem. 75, 134 (1971).
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The Ishikawa Problem - Limitations to Line Shape Analysis
ISHIKAWA (Tokyo Institute of Technology, Tokyo, Japan), a pioneer in organo-fluorine-chemistry,

synthesized 1,3,5-tris-(trimethylsilyl)-2,4,6-tri-fluorobenzene s-C6F3[Si(CH3)3]3, a silyl analogue of s-
trifluorobenzene s-C6H3F3.
Si(CH3)3 H
F F F F
(CH3)3Si Si(CH3)3 H H
F F
[AX9]3 [AX]3
While s-C6H3F3 gives rise to a well investigated [AX]3 system, s-C6F3[Si(CH3)3]3 is responsible for
1 19
rather complex A and X parts of a total [AXn]3 system (n = 9). Our experimental H and F NMR
spectra of s-C6F3[Si(CH3)3]3 are shown in the following graphics.
1 19
H NMR. Scale = 3.3 Hz. F NMR. Scale = 10 Hz.
X part A part
1 19
Figure 631 : H and F NMR spectra of s-C6F3[Si(CH3)3]3.
8 7
Our first guess assumed: long range couplings JAA´ = JHH = 0 Hz and JAX´ = JFH will be zero, while
5 4
JAX = JFH and JXX´= JFF will be non-zero. The latter parameter, a meta-FF coupling, was determined
to be 5.8 Hz in s-C6H3F3.
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841
The spin enumeration for the [AXn]3 system (n = 9) in s-C6F3[Si(CH3)3]3 is shown below.
Si(CH3)3 1
F F 6 2
(CH3)3Si Si(CH3)3 5 3
F 4
Parameters for [AXn]3 System of s-C6F3[Si(CH3)3]3

ν1 = ν 3 = ν 5 νX νH
ν2 = ν 4 = ν 6 νA νF
≠0
5
J12 = J23 = J34 = J45 = J56 = J16 JAX JFH
≠0
4
J24 = J46 = J24 JAA´ JFF
7
J14 = J25 = J36 JAX´ JFH =0
8
J13 = J35 = J15 JXX´ JHH =0
Parameters for [AXn]3 System of s-C6F3[Si(CH3)3]3

5 7
JAX = JFH = 1.65 Hz JAX´ = JFH = 0 Hz *
4 8
JAA´= JFF = 5.8 (assumption) ** JXX´ = JHH = 0 Hz *
) )
* assumption. ** data from 1,3,5-trifluorobenzene s-C6H3F3.
Didactical Studies with [AXn]3 Spectra for n = 1 to 5.
DAISY in the present version does not cover [AXn]3 cases with n > 5. The ISHIKAWA problem
spans a 30 spin system with n = 9. We cannot simulate this n = 9 problem, but learn to analyze this
spectrum partially.
For convenience ν A is set to -10 Hz, and νX to +10 Hz. Coupling parameters are set according
to: JAX = 1.65 HZ. JAA´= 5.8 Hz. JXX´ = 0 Hz. JAX´ = 0 Hz.
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842
An Part X Part
0.15 0.10 0.05 -0.00 -0.05 -0.10 -0.15

(ppm)
Figure 632 : [AXn]3. n = 1.
0.15 0.10 0.05 -0.00 -0.05 -0.10 -0.15

(ppm)
Figure 633 : [AXn]3. n = 2.
0.15 0.10 0.05 -0.00 -0.05 -0.10 -0.15

(ppm)
Figure 634 : [AXn]3. n = 3.
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0.15 0.10 0.05 -0.00 -0.05 -0.10 -0.15

(ppm)
Figure 635 : [AXn]3. n = 4.
0.15 0.10 0.05 -0.00 -0.05 -0.10 -0.15

(ppm)
Figure 636 : [AXn]3. n = 5.
We see deceptively simple spectra and find directly JAX (the proton-fluorine long range coupling
5 4
JFH) but not JAA´ (the meta fluorine-fluorine coupling JFF).
The A part of an [AXn]3 exhibits a (3n+1) line multiplet centered at νA with a repeated spacing of 2/3
of JAX.
If n is even, then a central line appears at νA. 3n/2 lines are symmetrically arranged to the left and
right of a central line located at νA.
If n is uneven, then (3n+1) lines are symmetrically arranged to the left and right of center νA.
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844
Figure 637 : A part of [AX3]3
The X part of an [AXn]3 exhibits a central line at ν3 = νX overlapped by a pseudo quartet (ν1, ν2, ν4,
ν5,) with a repeated spacing of 2/3 of JAX. Hence the difference of frequencies (ν1-ν5)
corresponds to 2 JAX.
Figure 638 : X part of [AX3]3
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845
JAA´ Influences the Spectral Pattern:
If JAA´ = 0, than the A part appears as a (2n-1) multiplet, while the X part will show a simple triplet.
Figure 639 : [AX3]3. JAA´ = 0.
Figure 640 : [AX3]3. JAA´ = JAX.
0.15 0.10 0.05 -0.00 -0.05 -0.10 -0.15

(ppm)
Figure 641 : [AX3]3. JAA´ = 2 JAX.
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846
0.15 0.10 0.05 -0.00 -0.05 -0.10 -0.15

(ppm)
Figure 642 : [AX3]3. JAA´= 3 JAX.
0.15 0.10 0.05 -0.00 -0.05 -0.10 -0.15

(ppm)
0.15 0.10 0.05 -0.00 -0.05 -0.10 -0.15

(ppm)
If the coupling constant JXX´ > 5 JAX then we see the spectral pattern shown above: the (3n+1)-line
and the 5-line patterns.
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The spectral half widths HWBA and HWBX influence the spectral patterns as well.
Hence iteration of [AXn]3 or sequential simulations with DAISY should lead to JAA´ wanted,
provided n is small enough.
But the Ishikawa problem is not solved yet by line shape analysis – due to the limitation of
large spin systems. In fact, it is not meaningful to do so. A faster, more time economic solution,
13 1 13 19 1
uses proton decoupling C{ H} or inspection of C satellites in F{ H}, which will yield the
parameter JXX´.
Si Si
F C* F F F
C*
Si Si Si Si
F F
2 1
JFC = JBX JFC = JBX
4 3
JFC = JAX JFC = JAX
4 4
JFF = JXX´ JFF = JXX´
AB2X A2BX
Those spectra are similar to AB2X or A2BX spectra obtained by analogous techniques from 1,3,5-
trifluorobenzene. See corresponding chapter on 4-spins and the 6-spin case of s-C6H3F3.
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24.5 Fourfold Symmetry in [AX3]4 ?
E. O. Fischer et al. characterized an interesting series of chromium(0) coordination compounds

[Cr(CO)6-n(PH3)n] (n = 1-4). [AX3]n type spectra were expected. But [Cr(CO)2(PH3)4] does not exist
with both CO ligands in trans conformation yielding the [[AX3]4 case. CO ligands are cis, thus
inducing an [AM3RX3]2 system:
CO PH3
PH3 PH3
H 3P Cr PH3 H 3P Cr PH3
H 3P OC
CO CO
E. Moser, E. O. Fischer, W. Bathelt, W. Gretner, L. Knauss, E. Louis; J. Org. Met. Chem. 19, 377-
385 (1969).
[Ni(PF3)4] has true tetrahedral symmetry and hence forms an [AX3]4 (Td) system. The compound
19 31
was synthesized by Nixon and Sexton but F and P NMR spectra showed insufficient fine
structure for spectral analysis. The simpler [AX]4 (Td) case was described for the proton decoupled
19 1 31 1
F{ H} and P{ H} NMR spectra for [Ni(RPF)4], where RPF stands for:
H O
P F
H O
Read:
a) J. F. Nixon, M. D. Sexton; J. Chem. Soc. (A) 1969, 1089-1091.
b) R. M. Lynden-Bell; Mol. Phys. 15, 523 (1968).
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24.6 End of the Flagpole: Problems that cannot be Fully

Analyzed and Simulated
- -
Octahedrally coordinated complexes with PF3 ligands like [V(PF3)6] or [Nb(PF3)6] are characterized
by [AX3]6M spin systems where M stands for quadrupolar nuclei V (I = 7/2) and Nb (I = 9/2) resp..
51 93
The 23.66 MHz of V and the 22.00 MHz Nb spectra basically appear as deceptively simple
1 1
binomial septets with splitting corresponding to JVP = 510 Hz and JNbP = 1050 Hz resp..
2
Superimposed are binomial multiplet structures (13 from 19 lines visible) due to JVF = 10.3 Hz and
2
JNbF = 55 Hz resp.. But the central [AX3]6 system cannot be fully analyzed, only a reasonable guess
1 - - 3 2 4
for JPF ([V(PF3)6] =1200 Hz; [Nb(PF3)6] =1250 Hz) but no data for JPF, JPP, and JFF were reported
by D. Rehder, H.-C. Bechthold, K. Paulsen; J. Magn. Res. 40, 305-310 (1980).
TopSpin and DAISY in the present state are not able to simulate spectra for those large spin
systems. DAISY can handle Oh symmetry but still the Hamilton Matrix is too large and cannot be
diagonalized.
The latter problems are beyond the scope of this manuscript, details will not be reported here.
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Samples, Solvents, Temperature
25 Samples, Solvents, Temperature
Here you will find some essentials concerning the necessary steps prior to practical measurements
of NMR spectra. Information on this topic is available from producers of NMR tubes and NMR
solvents and in a multitude of practical instructions from NMR labs in universities worldwide. One of
the best reports was written by A. S. F. Boyd in a document dated from 4 October, 1995. (NMR
Services at Heriot-Watt University Chemistry Dept., Edinburgh, Scotland).
In the following sections we have used this text and amalgamated it with details from our own
practical experience and other reports as indicated.
• How to Prepare Your Own Samples for Good NMR Spectra

In NMR spectroscopy the quality of samples has a profound effect on the quality of resulting
spectra. To ensure that the sample you prepare gives a spectrum in which useful information is not
lost or obscured, you must follow a few simple rules as given below.
• Use the Correct Quantity of Material

1
For H NMR spectra of organic compounds the quantity of material required is about 5 to 15 mg. It
is possible to obtain spectra from smaller quantities, but at very low concentrations, the peaks from
13
common contaminants such as water and grease tend to dominate the spectrum. C is six
1
thousand times less sensitive than H, and a good rule of thumb is to provide a minimum of 5 mg
per inequivalent carbon to achieve reasonable signal to noise in the spectrum. Obviously, the
higher the concentration the less time required to obtain the data. If about 0.2 to 0.3 millimoles can
be dissolved in 0.7 ml, the spectrum should take no more than about half an hour to record. If the
quantity of material is halved, the data accumulation time will be quadrupled. You should be aware
13 1
that if you make up a sample at high concentration for C and then record a H spectrum from it,
the increased solution viscosity may result in a spectrum that has broader lines than you would get
from a more dilute solution.
• Use Deuterated Solvents

Samples must be prepared using solvents that contain deuterium in place of hydrogen. The NMR
signal from the deuterium nuclei is called the NMR Lock and is used by the spectrometer for
stabilization of the magnetic field. Consider the cost of the solvents: reasonable prices have (1)
CDCl3 and C6D6 (2) everything else is more expensive. Because NMR solvents are costly
materials, deuterated solvents should be used with great care to minimize waste e.g. you must not
13 19 31
use them to do solubility trials. For certain experiments e.g. involving C, F, P, spectra can be
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1 1
obtained using a mixture of deuterated and non deuterated solvent. When observing H NMR or H
13 19 31
together with hetero nuclei like C, F, P etc., you must use fully deuterated solvents. A capillary
containing D2O or C6D6 etc. can be placed in the NMR tube when you do not wish to use internal
deuterated solvent. More accurate than an isolated capillary is a commercially available double
walled NMR tube, see below.
• Remove all Solid Particles

Solid particles distort the magnetic field homogeneity because the magnetic susceptibility of a
particle is different from that of the solution. A sample containing suspended particles thus has a
field homogeneity distortion around every single particle. This causes broad lines and indistinct
spectra that cannot be corrected. To ensure that there are no solid particles in your samples, you
must filter all samples into the NMR tube. Use the combination of a syringe (1 ml) together with a
micro filter (1 cm). After filtration the sample should be as clear as water though, of course, not
necessarily colorless. (Alternatively you may use a centrifuge in some suitable cases).
• Make Samples to the Correct Depth

In the magnet, the main field direction is vertical, along the length of the sample. Each end of the
sample causes a major distortion of the field homogeneity which is corrected using the
spectrometer's shim controls. A partial shim correction is done for every sample, and only takes a
few minutes. A complete shim correction can take several hours using a high quality test sample.
So that this lengthy task needs to be done as seldom as possible, it is best to prepare samples that
physically resemble the test sample. Therefore, after filtration; they must be made up to a similar
depth. This must be ~5 cm. Shorter samples are very difficult to shim, and cause considerable
delay in recording the spectrum. Samples that are too long also take time to shim and are a waste
of costly solvent. You should check your sample depth using a ruler. The sample depth for modern
cryoprobes is 4 cm. If in doubt, please contact your spectrometer manufacturer about the optimum
filling height for your probe.
Tubes must be capped (using clean caps). The cap is pushed fully onto the tube to minimize
solvent loss through evaporation. If your sample are sensitive towards humidity or oxygen, than
protect caps and upper end of NMR tubes by parafilm. High precision studies use vacuum
sealed NMR tubes after freeze-pump-thaw-techniques.
• Use Clean Tubes and Caps

NMR tubes should be rinsed with acetone or some other suitable solvent and then dried with a
blast of dry air or nitrogen. Do NOT dry tubes in a hot oven above 100°C because it does not
remove solvent vapor effectively, and solvent peaks will appear in your spectrum when using those
tubes. Also, NMR tubes are thin walled and drying in a hot oven may warp the tube leading to poor
rotation in the magnet.
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But you can dry your NMR tubes efficiently in vacuum. Clean NMR tubes, rinse with acetone
followed by diethylether and evacuate the tubes (simply use a trap attached to the vac line) to
effectively remove the vapors of solvents.
Some further Remarks on NMR Tubes
For reasonable NMR work, use NMR tubes in Research Quality. After buying the less expensive
routine NMR tubes make the banana test: roll the NMR tubes on a planar surface (e. g. glass
mirror). Select the tubes which roll smoothly indicating a linear cylindrical symmetry. Don’t use
tubes bent in “banana shape” - which do not roll smoothly on the mirror surface.
• Referencing
Using the selected tubes, you may decide between four techniques to set up your sample:
• Internal Referencing
Compound and reference are dissolved in a sample and transferred to the tube. Run NMR and see
1 13
in ONE spectrum compounds and reference. This is the routine technique in H and C NMR.
• External Referencing I
This method avoids compound-reference-interactions. Use an NMR tube with two coaxial
chambers. Fill solution with reference in outer ring and solution of compound in inner ring.
You may also use the outer ring for the pure deuterated solvent and the inner ring for a solution of
your compound in a non-deuterated solvent thus avoiding H-D-exchange reaction which will in
many cases occur when using the technique of internal referencing described above.
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Figure 645 : Coaxial NMR tubes. Right graphic from WILMAD.
• External Referencing II
Compound and reference are separately dissolved in identical solvents. Run two separate NMR
spectra and refer chemical shifts of compound to external sample. You may store the data for the
reference spectrum and use it for subsequent external referencing. This technique is often called
“Virtual Referencing”.
• Identifying and Labeling your Samples

Deliver your sample to the NMR service with a clear, complete and unique description of your
sample and spectra wanted.
• Do not Add Liquid TMS Directly to the Sample

The amount of TMS, or any other reference material, that is required for a proton NMR spectrum is
far less than can be added after the sample has been prepared. Even one drop of TMS in a sample
causes serious problems due to distorted baseline and exceeded dynamic range. If you wish to use
TMS as the reference, it is better to add a well defined quantity to the stock solvent. Alternatively,
the residual protons in the deuterated solvent may be used as a secondary reference. In practice
you may add gaseous TMS from a TMS bottle to a NMR tube using a syringe.
• Remove Oxygen from Sample by Freeze-pump-thaw Technique

If you want to acquire high precision (high resolution) NMR spectra, or if your samples are instable
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against oxygen and humidity, then seal your sample by micro-torch after applying the well known
freeze-pump-thaw technique (at least three cycles).
In many practical situations it is sufficient to flush the space above the sample surface with
nitrogen. This should be done with great care to avoid blowing the solution out of the tube. Do not
bubble nitrogen through the solution in an NMR tube. This wastes costly solvent and standard
through evaporation, and is not an effective method of removing oxygen. Good advice on NMR,
such as this by A. Boyd, can be found on the internet.
Some Comments on Standards in NMR Spectroscopy
Standards for 1H in Organic Solvents
• Tetramethylsilane TMS (CH3)4Si

1 13
(CH3)4Si is the routine standard for H, C and
29
Si NMR for which chemical shifts are defined: δH
= 0 ppm, δC = 0 ppm, and δSi = 0 ppm.
But having a low boiling point of 27°C TMS is not used for NMR studies at elevated temperatures.
For such purposes octamethylcyclotetrasiloxane [(CH3)2SiO]4 OMS may be used which is
characterized by a boiling point of 175°C and δH = 0.085 ppm.
Standards for 1H in Water
• 4,4-Dimethyl-4-silapentane-1-sulfonic Acid Sodium Salt

(CH3)3SiCH2CH2CH2SO3Na DSS also known as 3-trimethylsilyl-propane-sulfonic acid sodium
salt is used in proton- and carbon-related NMR spectroscopy as a calibration standard for aqueous
solutions (H2O and D2O). The proton spectrum of DSS exhibits a strong singlet corresponding to 9
protons from the trimethylsilyl group. In addition 3 multiplets appear around at 3.1 ppm (C-CH2-
SO3), 1.9 ppm (C-CH2-C), and 0,8 ppm (Si-CH2-C), each with an intensity of 22% of the reference
peak (CH3)3Si at 0.015 ppm. Those multiplets are due to a total of six protons from the α-, β- and
γ-methylene groups of the propane skeleton (forming an [ABC]2 system). Fortunately those peaks
appear much smaller in height than the reference singlet because of their multiplet structures.
We will discuss the corresponding [ABC]2 spectrum from -CH2-CH2-CH2- fragments at an advanced
level of this manuscript. The differences between chemical shifts of methylene groups and the
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terminal trimethylsilyl group depend on the pH of solution. 10 mg of DSS were dissolved in 0.5 ml
1
of a) 1 m KOD, b) D2O, c) 1 mDClO4. H NMR spectra were measured at 500 MHz.
Chemicals shifts given below are defined relative to the signal from the internal (CH3)3Si-C group
defined as δH((CH3)3)Si-C) = 0.
Signals δH of Signals in Solution

Signal 1 m KOD D2O 1 m DClO4
HOD 4.8928 4.7852 5.2031 [ppm]
-
C-CH2-SO3 2.9060 2.9064 2.9182 [ppm]
C-CH2-C 1.7488 1.7560 1.7507 [ppm]
Si-CH2-C 0.6201 0.6243 0.6276 [ppm]
(CH3)3Si Def = 0 Def = 0 Def = 0 [ppm]
1
As an example for those [ABC]2 multiplet structures the 500 MHz H NMR spectrum of DSS in D2O
is shown below:
C-CH2-SO3 C-CH2-C C-CH2-Si

2.9064 1.7560 0.6243
Figure 646 : 500 MHz H NMR spectrum of DSS. δH for -CH2- groups given in ppm.
1
1
If those multiplets peaks pose a problem in your H NMR spectra, a deuterated version of DSS
(CH3)3SiCD2CD2CD2SO3Na is available at much higher cost.
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Alternatively you may use:
• 3-(Trimethylsilyl)propionic Acid Sodium Salt

(CH3)3SiCD2CD2COONa TSP is a related compound used as an NMR standard exhibiting the
reference peak accurately at 0.000 ppm when dissolved in D2O. This carboxylic acid sodium has
two drawbacks when compared with the above mentioned sulfonic acid sodium salt:
a) it is less soluble in water
b) the carboxylic acid is weaker (higher pKa) than the stronger sulfonic acid.
Hence TSP is more prone to be affected by sample pH. While the sulfonate anion dominates, the
-
carboxylate anion R-COO is in protolytic equilibrium with the corresponding carboxylic acid
R-COOH in aqueous solutions. (The combination of NMR and protolytic equilibria was discussed in
more details in previous chapters).
• 4,4-Dimethyl-4-silapentane-1-ammonium-trifluoroacetate
+ -
[(CH3)3SiCH2CH2CH2NH3] [CF3COO] DSA has also been proposed as an alternative, to overcome
certain drawbacks of DSS.
For details see:

"DSA: A New Internal Standard for NMR Studies in Aqueous Solution". J. S. Nowick, O.
Khakshoor, M. Hashemzadeh, and
J. O. Brower. Org. Lett. 5 (19): 3511–3513 (2003). doi:10.1021/ol035347w.
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Additional Notes on 1H Standards from the Bruker Almanach
Silylated Compounds Used as Proton References
Chemical Shift Ranges and Standards for Selected Hetero Nuclei
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19
Selected Standards for Hetero Nuclei F
δF [ppm]
Trichlorofluoromethane CFCl3 0.0
1,1,2,2-Tetrachloro-3,3,4,4-tetrafluorocyclobutane C4F4Cl4 -114.2
Hexafluorobenzene C6F6 -163.3198
19
CFCl3 is a less suitable reference but still used in NMR practice for historical reasons. A F NMR
spectrum measured with modern high field supercon magnets reveals clearly that CFCl3 is
characterized not by one singlet but by the superposition of four singlets originating from the four
35 35 37 35 37 37 19
isotopomeric molecules CF Cl3, CF Cl2 Cl, CF Cl Cl2, and CF Cl3. The second F NMR peak
(from left) corresponds to CF Cl2 Cl, and this is the resonance which is actually defined to δF =
35 37
0.0 ppm.
Frequencies by Peak Picking

-0.00
-2.86
-5.91
2.95
10 5 0 -5 -10
(Hz)
19 35 35 37 35 37 37
Figure 647 : F NMR spectrum showing CF Cl3, CF Cl2 Cl, CF Cl Cl2 and CF Cl3.
Frequencies by Deconvolution
No. Position Position Position Width Width Intensity Integral
(Hz) (Hz) (ppm) (Hz) (ppm) (rel.)
1 +0.28 +3.02 +0.0006 1.27 0.0027 5.494160e+003 45.40
2 -2.74 0.00 -0.0058 1.23 0.0026 5.269637e+003 42.34
3 -5.73 -2.99 -0.0122 1.16 0.0025 1.566528e+003 11.86
4 -8.76 -6.02 -0.0186 0.45 0.0010 1.373817e+002 0.40
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The case of CFCl3 is discussed in more details in chapter 5.1 of this manuscript.
In 1,1,2,2-Tetrachloro-3,3,4,4-tetrafluorocyclobutane C4F4Cl4 the fluorine atoms are more

distant towards the chlorine atoms. Hence the isotope effect is less pronounced. A sharp singlet
line results, which may serve as a good secondary reference. The chemical shift δF is set to -114.2
ppm vs. CFCl3. Since δF is sensitive to concentration, solvent, and temperature it is advisable to
make your own reference data: choose your typical solvent, add small amounts of CFCl3 and
1,1,2,2-C4Cl4F4 and measure the resonance frequencies (chemical shifts) of both fluorine signals.
Hexafluorobenzene C6F6 (dissolved in C6D6 together with a trace of CFCl3) gives rise to a singlet
at δF = -163.3198 ppm vs. int. CFCl3. It may be used as secondary reference when studying
fluorinated compounds with resonances around that region.
Selected Standards for Hetero Nuclei 31P
31
Up to now no reliable internal references for P NMR are known. Resonances from esters like
P(O)(OCH3)3, CH3P(O)(OCH3)2, and similar are solvent dependent. Acids like H3PO4, H3PO3,
CH3PO3H2 are subject to protolytic equilibria in aqueous solutions and hence variable in δP with pH
of solution. Internationally accepted is 85% H3PO4. It serves as external standard and as virtual
standard - despite of its broad line width.
An interesting observation was made by T. Glonek (J. Magn. Reson. 13, 390-391 (1974)).
A 0.2 m solution of H3PO4 in aqueous 14% HClO4 shows a sharp line at -0.067 ppm.
+
The corresponding signal is due to the tetrahydroxiphosphononium cation P(OH)4 as shown in the
following figure:
31
40.48 MHz P NMR spectrum of 85% phosphoric acid (broad signal) externally referenced to
aqueous tetrahydroxyphosphonium perchlorate (sharp signal).
31
This observation did not lead to the definition of an accepted novel standard for P NMR.
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Some Comments on Solvents
Solvents
1
For H experiments on conventional organic compounds involving H-C bonds protonated solvents
should be avoided, if possible, as the strong solvent signals will interfere with the spectrum
required. (Solvent suppression [HMG] experiments can sometimes be used to reduce solvent
1
signals in H spectra). The solvent should normally contain a strong deuterium signal (e.g. CDCl3)
so that the field can be "locked" for the duration of the experiment. This is especially important for
1
H measurements where resolution is required.
31 11
Spectrometers have an option for running samples unlocked e. g. for P or B measurements.
The magnetic field of a good supercon magnet is sufficiently stable to allow even for longer (24 h)
unlocked measurements. In such cases protonated solvents suffice and costly deuterated solvents
may be avoided.
Generally
• Always use the least expensive solvent compatible with your sample.
• Alternatives with similar solubility properties are: Benzene C6D6 instead of toluene C6D5CD3,
acetone CD3COCD3 instead of acetonitrile CD3CN / methanol CD3OD / dichloromethane
CD2Cl2.
• Routine H spectra are unlikely to justify the use of an expensive solvent. H NMR
1 1
measurements are so sensitive, that using a more dilute solution because of limited solubility is
often wiser than using an expensive solvent.
• Mixtures of protonated and deuterated-solvents may be used to reduce costs (except where H
1
spectra are required!). e.g. a solution of 20% CD2Cl2 in CH2Cl2 is suitable for use on all
instruments. However, do not use CDCl3/CHCl3 mixtures if commercial CHCl3 contains ethanol
as a stabilizer and CDCl3 is cheap.
• Never run a sample without reference. Always add TMS (as vapor) unless using the special
solvent CDCl3 with TMS already added. It is convenient to define a problem specific cocktail for
your experiments holding solvent, lock and references at low concentrations. The reference
signal should be smaller than the maximum of your sample´s signal. This precaution avoids
problems with digital resolution of intensities (the y-axis of your spectrum).
Chemical Shifts for Residual Peaks in Typical Deuterated Solvents

Completely deuterated solvents are very difficult to make and expensive. In almost all cases,
residual protons in the deuterated solvent will cause a resonance peak (or peaks) to appear in the
spectrum. The following table shows the chemical shift values for the more common solvents used
1
for H NMR spectroscopy.
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Overview of Residual Peaks in Deuterated Solvents
Chemical Shifts for Water Peaks in Typical Deuterated Solvents

1
Water peaks are observed quite frequently in H NMR spectra. Those peaks (appearing as broader
lines) are due to humidity in air, solvent, compound, and NMR tubes. Chemical shifts of water
peaks depend on polarity of solvents, concentration and temperature of samples (VT-NMR
experiments).
In some cases two water peaks are observed corresponding to separate H2O and HOD signals. In
acetone-d6 the H2O peak appears at 2.82 ppm while HOD resonates at 2.78 ppm giving rise to a
2
1:1:1 three line system exhibiting the coupling H-O-D with JDH = 2.07 Hz, see the next figure.
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1
Figure 648 : H NMR spectra showing separate HOH and HOD peaks. See text.
In CDCl3 the H2O and HOD resonances are shifted to high field resonating around δH 1.52 ppm
and 1.49 ppm resp. See right figure above. Double water peaks were observed in the early days of
NMR, but this phenomenon is overlooked occasionally nowadays.
J. Holmes, D. Jivelson and W. Drinkard (J. Chem. Phys. 37, 150 (1962)) reported an equilibrium
constant of 4.0 ± 0.4 for the proton deuteron exchange in acetone solutions:
H2O + D2O = 2 HOD
2
The HOD triplet with JDH = 1.1 ± 0.1 Hz) is centered 0.030 ± 0.003 ppm to higher field relative to
the H2O singlet. Addition of a trace of HCl induces a break-down of the triplet structure as a result
of the rapid proton and deuteron transfer reactions.
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A list of chemical shifts of water peaks from commercial deuterated solvent is given in the
subsequent table.
Deuterated Solvents – Relevant Properties
Residual Water 13
C NMR
peak peak
Solvent Formula m.p. b.p. δH δH δC
o o
[ C] [ C] [ppm] [ppm] [ppm]
Chloroform-d1 CDCl3 -64 62 7.25-7.26 1.55 77.0
Methylenchloride-d2 CD2Cl2 -95 40 5.32 1.52 53.8
1,1,2,2-Tetrachloroethane-d2 C2D2Cl4 -45 145 5.91 1.5 74.2
Water-d2 D2O 3.8 101.4 4.67-4.82 - -
1.3
Acetonitrile-d3 C2D3N -45 82 1.93 2.12
118.2
Nitromethane-d3 CD3NO2 -29 101 4.33 2.20 62.8
3.30-3.31
Methanol-d4 CD4O -98 65 4.85 49.0
4.78
2.03 20.1
Acetic acid-d4 C2D4O2 17 118 -
11.53-11.7 178.4
123.5
7.50
129.5
Nitrobenzene-d5 C6D5NO2 6 211 7.61 2.42
134.8
8.11
148.6
7.19 123.5
Pyridine-d5 C5D5N -42 116 7.55 4.95 135.5
8.71 149.9
2.81- 29.8
Acetone-d6 C3D6O -94.7 56.1 2.04-2.09
2.84 206.0
Dimethylsulfoxide-d6 C2D6OS 18 189 2.49 3.30 39.5
1.11
17.2
Ethanol-d6 C2D6O -117 78.3 3.56
56.8
5.19
Benzene-d6 C6D6 5 80 7.15 0.4 128.0
2.74 30.1
Dimethylformamide-d7 C3D7NO -61 153 2.91 3.45 35.2
8.01 162.7
25.2
Tetrahydrofurane-d8 C4D8O -109 66 3.53
67.4
1.73
1.4-Dioxane-d8 C4D8O2 12 101 2.45 66.5
3.58
20.4
2.09
125.2
6.98
Toluene-d8 C7D8 -95 111 0.5 128.0
7.00
128.9
7.09
137.5
δH [ppm] vs. TMS or TSP resp.
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Fluorinated Solvents
Residual Water 13
C NMR
peak peak
Solvent Formula m.p. b.p. δH δH δC
o o
[ C] [ C] [ppm] [ppm] [ppm]
Trichlorofluoromethane CFCl3 -111 23.7 none 117.6
-15.3 72.4 3.88 61.5
2,2,2-Trifluoroethanol-d3 CF3CD2OD
5.02 126.3
-15 72 ca. 12 116.5
Trifluoroacetic acid-d1 CF3COOD
164.4
Non-deuterated Solvents
Solvent Formula
m.p. b.p. δH δC
°C °C ppm ppm
Carbon disulphide CS2 -11.6 46.3 none 192.8
Carbon tetrachloride CCl4 -23.0 76.8 none 96.7
Diethyl ether (CH3CH2)2O -116.3 34.6 66.51*
Dimethyl ether (CH3)2O -138.5 -23 3.2 60.08*
1,4-Dioxane C4H8O2 11.8 101.4 3.53 66.7*
Tetrahydrofurane C4H8O 67.96*
*) δC(-O-C-) at -100 °C.
For more details and actual spectra see:

NMR Chemical Shifts of Common Laboratory Solvents as Trace Impurities, H. E. Gottlieb, V.
Kotlyar, A. Nudelman; J. Org. Chem. 62, 7512-7515 (1997)
1
CD2Cl2 contains traces of CHDCl2 and even minute amounts of CH2Cl2. The residual peaks in H
NMR of CHDCl2 represent the characteristic 3-line pattern with intensities 1:1:1 while CHCl3 simply
yields a singlet.
Commercially available CD3 substituted compounds such as CD3CN, CD3OD, CD3COOD,

CD3COCD3, and CD3SOCD3 will contain isotopomers holding CHD2 and even traces of CH2D units.
The CHD2 fragment is characterized by a 5-line pattern with 1:2:3:2:1 intensity ratio while the CH2D
gives rise to the 1:1:1 multiplet mentioned above. We will discuss spectral patterns involving nuclei
with spins > 1/2 at an advanced level of his manuscript. Two experimental examples are shown
below.
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1
Residual Peaks in H NMR Spectra of Commercial CD2Cl2 Solvent:
CHDCl2 and CH2Cl2
1
Figure 649 : H NMR signals from CHDCl2 and CH2Cl2 in commercial CD2Cl2.
Species Peak picking Deconvolution

CH2Cl2 δH 5.2480 5.249 [ppm]
CHDCl2 δH 5.2355 5.236 [ppm]
2
CHDCl2 JDH 1.07 1.11 [Hz]
1
Figure 650 : Peak Picking H NMR signals from CHDCl2 and CH2Cl2 in CD2Cl2.
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1
Figure 651 : Lorentzian Deconvolution H NMR signals from CHDCl2 and CH2Cl2 in CD2Cl2.
Species δH νH HWB HWB Intensity Area

ppm Hz ppm Hz rel %
CH2Cl2 5.249 1050.39 0.00178 0.357 3.791 8.463
CHDCl2 5.242 1049.02 0.00171 0.342 14.689 31.452
CHDCl2 5.236 1047.93 0.00209 0.417 12.802 33.446
CHDCl2 5.231 1046.81 0.00190 0.380 13.511 32.160
Commercial dimethylsulfoxide-d6 contains traces of CHD2-SO-CD3 (and minute amounts of

CH2D-SO-CD3). The CHD2-group gives rise to the characteristic 5-line pattern shown below:
1
Figure 652 : H NMR spectrum of dimethylsulfoxide-d6. Main signal (right): 5-line pattern of CHD2-SO-
CD3. Weak signal (left): 3-line pattern from CH2D-SO-CD3
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An analogous pattern is observed for CHD2-CO-CD3 from commercial acetone-d6 revealing
parameters δH = 2.04 ppm, JDH = 2.11 Hz.

2
Obviously - in unlucky cases - residual peaks from incompletely deuterated solvents may obscure
signals from your sample. This problem can be overcome in two ways by:
a) increasing the concentration of your compound,

b) increasing the concentration of the fully deuterated solvent.
The latter implies buying solvents with higher degrees of deuteration at higher costs.
Useful advice is given by NMR-Solvents – Online:
13 13
Analogous reasonings hold for C NMR studies: natural abundance of C (ca. 1%) gives rise to
13 12
C peaks from NMR solvents. For special studies (costly) C enriched solvents are available.
Example:
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1
The H NMR chemical shift of the HOD peak depends on temperature.
1
HOFFMAN recorded the H spectrum of a sample of commercially available D2O as a function of
temperature. The experimental sample contained a crystal of sodium 3-trimethylsilyl-propane-
sulfonate (CH3)3Si-CH2-CH2-CH2-SO3Na DSS as reference. The chemical shift δH(HOD) is defined
by:
ν (HOD) -ν H (DSS)
δH (HOD) = H
ν H (DSS)
δH(HOD) follows the equation:
δ H (HOD)=5.066 - 0.0112 t + 0.0000211t 2
which reproduces the measured values to better than 0.001 ppm. Parameters used: δH = chemical
shift [ppm]; t = temperature [°C].
For the more limited range form 0 to 50°C a simplified equations suffices,
δ H (HOD)=5.011- 0.0111t
which reproduces the experimental data to better than 0.01 ppm.

For details see: R. E. Hoffman; Magn. Reson. Chem. 44, 606-616 (2006).
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The HOD peak indicates the dynamic average of chemical shifts for cationic, neutral and anionic
species in equilibria.
H3O+ H 2O HO-
H2DO+
HOD
HD2O+
D3O+ D 2O DO-
Figure 653 : Horizontal: proton / deuteron exchange. Vertical: protium / deuterium exchange.
including additional solvation effects. Hence the HOD peak will be influenced as well by protolytic
(deuterolytic) equilibria, e. g. reflected by the pH (pD) of solution. Bear this in mind when defining
the exp. conditions of your NMR sample!
How Reliable is a Standard?
HOFFMAN performed an excellent study on the temperature dependence of standard signals in a

variety of deuterated solvents. Results may be important for your own experimental work.
Read details in: Magn. Reson. Chem. 44, 606-616 (2006).
See also an excellent paper on

1
“Temperature dependence of the H NMR chemical shift of tetramethylsilane in chloroform,
methanol and dimethylsulfoxide” published by
R. E. Hofmann and E. D. Becker; J. Magn. Reson. 176, 87-98 (2005).
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Determining Temperature in Samples during 1H und 2H NMR Experiments
Interesting and accurate work was done by A. L. van Geet. Read the following papers:
a) Inorg. Chem. 7, 2026 (1968)

b) Anal. Chem. 40, 1914 (1968)
c) Anal. Chem. 40, 2227-2229 (1968)
The difference ∆H in chemical shifts δH(CH3) - δH(OH) [ppm] from protio methanol CH3OH depends
significantly on the temperature [°K] following equation
T = 435.5 -1.193*60* ∆H -29.3*36* ∆H

2
This quadratic fit of experimental data covers the range from 220°K to 330°K and is affiliated with
an accuracy expressed as rms of 0.6°K.
For restricted ranges of temperature linear data fitting suffices:
220°K-280°K T = 478.6 - 1.906*60* ∆H rms = 0.8°K
260°K-320°K T = 464.0 - 1.775*60* ∆H rms = 0.4°C
Similar results were found for glycol HOCH2CH2OH. The difference in chemical shifts [ppm]
∆H = δH(CH2) - δH(OH)
is used to determine the temperature T [°K]
T = 466.0 - 1.694*60* ∆H
d) Rev. Sci. Instrum. 40, 177 (1969)

e) Anal. Chem. 42, 679-680 (1970)
A trace (0.03 vol %) of concentrated hydrochloric acid was added to air saturated methanol. This
causes a complete collapse of multiplet structures (by rapid exchange of the hydroxyl proton) to
1
yield neat singlets for CH2 and COH resonances. We will see at an advanced level that the H
NMR spectrum of dry glycol corresponds to a complex 6-spins system of [[A]2]X]2 type.
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This sample follows equation:
T = 403.0 – 0.491*60* ∆H - 66.2*36* ∆H

2
1
Some comments concerning the temperature dependence of H NMR shifts of DSS, TSP and
tetramethylammoniumchloride in aqueous solutions were given by B. P. Cross and T. Schleich
(Org. Magn. Res. 10, 82-85 (1977)).
The 99.8% Deuterated Methanol 1H NMR Thermometer
0.03 vol% of conc. HCl and 6.0 vol% TMS were added to 99.8% deuterated Methanol. Signals for
the residual CHD2 and COH groups were monitored at 200 MHz as functions of temperature to
yield the following equations:
a) νH(CHD2) = 653.8 + 0.203 t +0.00007285 t2 rms = 0.16 Hz
b) νH(COH) = 61295.3 -0.336 t -0.002511 t2 rms = 1.21 Hz
introducing
∆H = νH(COH)-νH(CHD2)
leads to a total fit of
t = 398.7 - 0.1347 ∆H - 0.0006109 ∆H

2
c) rms = 0.69 °C
which is consistent with the van Geet expression shown above.
Read details in: E. W. Hansen; Anal. Chem. 57, 2993-2994 (1985).
Hoffman investigated deuterated methanol and protio-glycol and described results in a neat
notation as given below. The temperature t [°C] was measured from the chemical shift separation
D
∆δ of deuterium in CD3OD or H∆δ from protons in HOCH2CH2OH:
D
∆δ = δD(OD)-δD(CD3) CD3OD
H
∆δ = δH(OH)-δH(CH2) HOCH2CH2OH
t(CD3OD) = -14.68 (
D
∆δ)2 – 65.06 D∆δ +159.48 + 3.8*10-15 exp(-13.2 D∆δ)
t(HOCH2CH2OH) = -3.22 (
H
∆δ)2 – 97.58 H∆δ +191.87
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The latter equation was calibrated against a combination of CD3OD and previously published glycol
scales:
t(HOCH2CH2OH) = -2.80 (
D
∆δ)2 – 98.26 H∆δ +189.71
For details see: R. E. Hoffman; Magn. Reson. in Chem. 44, 606-616 (2006).
See also references quoted herein: R. E. Hoffman and E. D. Becker; J. Magn. Reson. 178, 87
(2005). C. Ammann, P. Meier, A. E. Merbach; J. Magn. Reson. 48, 319 (1982).
M. L. Kaplan, F. A. Bovey, H. N. Chenf; Anal. Chem. 47, 325 (1975).
Determining Temperature in Samples during 13C NMR Experiments
An interesting method to determine temperature inside NMR samples uses the clearing points of a
1 13
series of commercially available liquid crystals. This method is suitable for H and C NMR.
1 13
Accuracies are ± 0.2°C for H NMR and ± 0.3°C for C NMR. The calibration of the glycol NMR
thermometer was re-examined.
For details see: H. Friebolin, G. Schilling and J. Pohl; Org. Magn. Res. 12, 569-573 (1979).
C NMR indicator for temperature t [°C] is the difference of chemical shifts ∆C [ppm] from
13
A good
the COOH and the CHCl2 carbons in pure dichloroacetic acid. Using
∆C = δC(COOH)-δC(CHCl2)
the following equations were found:
∆C = 106.88 - 0.01856 t
t = 5758.4 - 53.878 ∆C
Warning: ∆C decreases with increasing content of water in dichloroacetic acid.

For details read: L. D. Field, S. Sternhell and W. Veigel; Org. Magn. Res. 22, 221-223 (1984).
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Determining Temperature in Samples during 19F NMR Experiments
A mixture consisting of 98 vol % of CF3-CCl=CCl2 and 2 vol % of CFCl2-CFCl2 may serve as useful
indicator for temperatures within a range of -45°C and +90°C.
Defining the absolute value of the difference of chemical shifts ∆ [ppm] by:
∆ = δF(CF3-CCl=CCl2) − δF(CFCl2-CFCl2)
a linear function for the temperature [°C] was found
t = 555.0 – 86.305 ∆
This empirical equation is characterized by a root mean square deviation of 0.33°C or the
separation of chemical shifts ∆ by 0.00367 ppm resp..

For details read: N. Muller and T. W. Johnson; J. Phys. Chem. 73, 2460-2461 (1969).
19
A similar F NMR thermometer for a range from -10°C to -110°C was developed using CFCl3 and
CF2 =CCl2. For details read: R. A. Newmark and R. E. Graves; J. Phys. Chem. 72, 4299 (1968).
1 13 19
Multinuclear NMR Thermometers were Described Combining H, C and F NMR.
No. C6H5CH3 C6F6 CHFCl2 C6D5CD3 Observables

[ml] [ml] [ml] [ml]
1 0.50 0.25 5.00 0 δH(C6H5)-δH(CHFCl2), δF(C6F6)-δF(CHFCl2)
2 0 0.25 5.00 0.50 δF(C6F6), δH(CHFCl2), δc(CD3)
For graphs/tables see: J. Bornais and S. Brownstein; J. Magn. Res. 29, 207-211 (1978)
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Chiral Solvents - Observation of Solvation Diastereomers by 94.1 MHz 19F NMR
2,2,2-trifluoro-1-phenyl-ethanol (1) and α-(1-naphthyl)-ethylamine (2) were mixed in a ratio of 1:2.
OH NH2
C CF3 C CH3
H H
1 2
NMR samples were prepared from this mixture and additional ca. 75 mol% of CFCl3 as a cosolvent,
reference and lock.
If the alcohol (1) and the amine (2) both are racemic a simple pattern was observed by 94.1 MHz
19 3
F NMR.: a doublet of triplets. The doublet splitting corresponds to JFH = 6.8 Hz while the triplet is
5
due to long range coupling JFH < 0.5 Hz between the fluorines in the CF3-group and the pair of
ortho-protons of the phenyl unit, see the left figure below:
19
Figure 654 : Left: 94.1 MHz F NMR spectrum from a mixture of rac 2,2,2-trifluoro-1-phenyl-ethanol (1)
and rac α-(1-naphthyl)-ethylamine (2). Right: rac 2,2,2-trifluoro-1-phenyl-ethanol (1) and d-α-(1-
naphthyl)-ethylamine.
If the alcohol (1) is racemic but the amine (2) is pure d-α-(1-naphthyl)-ethylamine the above
mentioned pattern is duplicated: solvation induced diastereomers are observed where shifts δF are
separated by 0.053 ppm, see the right figure above.
The method of solvation induced diastereomers can be expanded to determine the ratio of optically
active substrates.
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NMR Frequencies for Some Selected Nuclei
Practical examples of simple and complex NMR spin systems discussed within this manuscript will
1 13 19 31
mainly deal with nuclei of type H, C, F and P as commonly used in pharmaceutical, organic
and inorganic chemistry. Some examples from inorganic chemistry will also hold more rare spin
types as listed in the following tables.
1
A comprehensive description of nuclear properties and NMR (excluding the more common H and
13
C) is given by R. K. Harris and B. E. Mann; “NMR and the Periodic Table”. Academic Press,
London, 1978.
Pure Elements with Spins I
1/2 1 3/2 2 5/2 3 7/2 4 9/2

19 9 27 45 93
F Be Al Sc Nb
31 23 55 133 109
P Na Mn Cs Bi
103 75 59 165
Rh As Co Ho
169 159 127
Tm Tb I
197 141
Au Pr
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Other Mixed Elements with Spins I
1/2 1 3/2 2 5/2 3 7/2 4 9/2

1 2 7 17 10 47 83
H H Li O B Ti Kr
3 14 11 51 49 179
H N B V Ti Hf
13 33 67 91
C S Zn Zr
15 35 85 139
N Cl Re La
29 37 86 177
Si Cl Re Hf
57 39 95 181
Fe K Mo Ta
107 53 97
Ag Cr Mo
109 63 99
Ag Cu Ru
111 65 101
Cd Cu Ru
113 67 105
Cd Ga Pd
113 71
Sn Ga
115 79
Sn Br
123 81
Te Br
125 131
Te Xe
129 189
Xe Os
183 191
W Ir
187 193
Os Ir
195 199
Pt Hg
199
Hg
203
Tl
205
Tl
207
Pb
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Practically Relevant Nuclei for Examples within this Manuscript
Iso Type % I Q Frequency Frequency

1 H 99.98 1/2 0 200.042 500.130
13 C 1.11 1/2 0 50.003 125.758
15 N 0.37 1/2 0 20.479 50.697
19 F 100 1/2 0 188.237 470.592
29 Si 4.7 1/2 0 39.730 99.362
31 P 100 1/2 0 80.982 202.456
129 Xe 26.4006 1/2 0 55.6348 139.087
2 D 0.0156 1 0.286 30.709 76.773

10 B 19.0 3 8.46 21.493 53.732
11 B 80.1 3/2 4.06 64.149 160.462
17 O 0.037 -5/2 -2.56 27.120 67.800
NMR Frequencies Normalized to νH = 200.000 and 500.00 MHz Resp.
Iso Type Frequency Frequency

1 H 200.000 500.000
2 D 30.701 76.753
13 C 50.288 125.721
19 F 188.154 470.385
31 P 80.961 202.404
Exercise:
1
An old 60 MHz H NMR spectrum used for the calibration of chemical shifts vs. TMS might still be
useful for didactics. See: Jungnickel; Anal. Chem. 35, (12) 1987 (1963)
1
Figure 655 : 60 MHz H NMR of a mixture of characteristic compounds. For data see text.
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Chemical shifts δH [ppm] and resonance frequencies νH [Hz] vs. TMS were measured at 37°C. In
addition temperature coefficients ∆t / /∆ν [°C/Hz] are given in a table below:
Compound Compound Vol % δH νH ∆t / /∆ν

CHCl3 Chloroform 18 7.3303 439.82 -0.052
CH2Cl2 Methylenechloride 8 5.3010 318.06 -0.036
C4H8O2 1,4-Dioxane 2 3.6207 217.24 -0.025?
CH3CCl3 1,1,1-Trichloroethane 9 2.7307 163.84 -0.020
C2H6O Acetone 3 2.1120 126.72 -0.046
C6H12 Cyclohexane 2 1.4330 85.98 -0.008
TMS Tetramethylsilane 3 0 0 -o
1
Make an analogous sample and re-measure the H NMR spectrum on your local NMR
spectrometer. The result should look similar to :
7 6 5 4 3 2 1 0
(ppm)
1
Figure 656 : The hypothetical H NMR spectrum from a mixture of CHCl3, CH2Cl2, C4H8O2, CH3CCl3,
C2H6O, C6H12, and TMS (from left to right), using an "equivalent concentration of protons" for each
component.
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How to Present NMR Data in Literature – Read the Definitions:
“Standard Definitions of Terms, Symbols, Conventions, and References Relating to High-

Resolution Nuclear Magnetic Resonance (NMR) Spectroscopy”. Annual Book of ASTM Standards,
Amer. Soc. For Testing and Materials, Designation E 386 – 76 (1976).
“Presentation of NMR Data for Publication in Chemical Journals - A”. Pure Appl. Chem. 29, 627
(1972). This section A deal with NMR Spectra from Protons.
International Union of Pure and Applied Chemistry. Recommendations for the Presentation of NMR
Data. “Presentation of NMR Data for Publication in Chemical Journals - B. Conventions Relating to
Spectra from Nuclei other than Protons”. Org. Magn. Res. 11, 267 (1978).
International Union of Pure and Applied Chemistry. “Parameters and symbols for use in Nuclear
Magnetic Resonance”. Pure & Appl. Chem. 69, 2489-2495 (1997).
Recent definitions and valuable reading are found in the following paper:
International Union of Pure and Applied Chemistry. “Further conventions for NMR Shielding and
Chemical Shifts”. Pure & Appl. Chem. 80, 59-84 (2008).
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Number of Transitions for Coupled Systems
26 Number of Transitions for

Coupled Systems of Spins I = ½.
Some General Expressions
Number
System Number of Transitions Valid for Part
of Spins
ABCD…Z n spins ( )
2n
n−1
for ABCD…Z
( )
2n
2 n−1
for ABCD….Z part
ABCD…ZX n+1 spins
( )
2n
n for X part
4(p + 1)(q + 1) for AB part
ABMpXq 2+p+q spins 2(q + 1)(2p + 1) for M part
2(p + 1)(2q + 1) for X part
Explicit Expressions - 1 to 3 Spins
Number of Spins Spin system Number of Transitions

All n An 1
2 AB 4
3 ABC 15
3 ABB´ 15
3 ABX 14
3 AXX´ 13
3 AB2 9
3 AX2 5
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Number of Transitions for Coupled Systems
The Maximum Number of Transitions in Spectra from Systems with 4 to 7 Spins
Number of Spins Spin System Number of Transitions

4 ABCD 56
4 ABXY 48
4 ABC2 34
4 AB2X 30
[AB]2 24
[AX]2 20
4 A2B2 18
4 AB3 16
4 A2X2 6
5 ABCDE 210
5 ABCD2 128
[AB]2C 110
[AB]2X 95
[AX]2B 88
5 AB2C2 78
5 ABC3 61
5 A2B3 37
5 AB4 25
6 ABCDEF 495
6 ABC2D2 195
6 ABCD3 155
6 A2B2C2 123
6 AB2C3 97
6 A3B3 48
6 A3X3 8
7 AB6 49
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Lorentzian Line Shape of a Singlet
27 Lorentzian Line Shape of a Singlet
Absorption and Dispersion Modes - Corresponding Derivatives of First to Fourth Order
The Intensity A The Intensity D

of the Absorption Mode of the Dispersion Mode
T2 2πT22 (ν 0 − ν )
A= D=
1 + 4π2T22 (ν 0 − ν )2 1 + 4π2T22 (ν 0 − ν )2
The First Derivative A´ The First Derivative D´
8 π2T23 (ν 0 − ν ) 2 π2T22 [4π2T22 (ν 0 − ν )2 − 1]

A´ = D´ =
[1 + 4π2T22 (ν 0 − ν )2 ]2 [1 + 4π2T22 (ν 0 − ν )2 ]2
The Second Derivative A´´ The Second Derivative D´´
8 π2T23 [12π2T23 (ν 0 − ν )2 − 1] 16 π3T24 (ν 0 − ν )[4π2T22 (ν 0 − ν )2 − 3]

A´´ = D´´ =
[1 + 4π2T22 (ν 0 − ν )2 ]3 [1 + 4π2T22 (ν 0 − ν )2 ]3
The Third Derivative A´´´ The Third Derivative D´´´
+ 384 π4 T25 (ν0 − ν)[4 π2 T22 (ν0 − ν)2 − 1] 48π3T24 [16π4T24 ( ν 0 − ν )4 − 24π2T22 ( ν 0 − ν )2 + 1]
A´´´ = D´´´ =
[1+ 4 π2 T22 (ν0 − ν)2 ]4 [1 + 4π2T22 (ν 0 − ν )2 ]4
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Absorption: Singlet Centered at ν = 0 Hz, Spectral Half Width HWB = 1 Hz, T2 = 1/(πHWB)
Red A Absorption
Blue A´ First Derivative of Absorption
Green A´´ Second Derivative of Absorption
Brown A´´´ Third Derivative of Absorption
Figure 657 : Absorption: singlet centered at ν = 0 Hz, spectral half width HWB = 1 Hz. 1
rst rd
to 3
derivatives.
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Special Points of Functions:
Zero ν Max ν Min ν
A0 ν=±∞ Amax ν = ν0 Amin ν=±∞
ν=±∞ 3
A´0 A´max 3 A´min ν = ν0 +
ν = ν0 ν = ν0 − 6πT2
6πT2
ν=±∞
1
A´´0 3 A´´max ν = ν0 ± A´´min ν = ν0
ν = ν0 ± 2πT2
6πT2
ν=±∞ 2 2
1− 5 1− 5
ν = ν0 + 5 ν = ν0 − 5
2πT2 2πT2
ν = ν0
A´´´0 A´´´max A´´´min
2 2
1+ 5 1+ 5
1 ν = ν0 − 5 ν = ν0 + 5
ν = ν0 ± 2πT2 2πT2
2πT2
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Dispersion: Singlet Centered at ν = 0 Hz, Spectral Half Width HWB = 1 Hz, T2 = 1/(πHWB)
Red A Dispersion
Blue A´ First Derivative of Dispersion
Green A´´ Second Derivative of Dispersion
Brown A´´´ Third Derivative of Dispersion
Figure 658 : Dispersion: singlet centered at ν = 0 Hz, spectral half width HWB = 1 Hz. 1
rst rd
to 3
derivatives.
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Special Points of Functions:
Zero ν Max ν Min ν
ν = ν0 1 1
D0 Dmax ν = ν0 − Dmin ν = ν0 +
ν=±∞ 2πT2 2πT2
ν=±∞
3
D´0 D´max ν = ν0 ± D´min ν = ν0
ν = ν0 ±
1 2πT2
2πT2
ν = ν0 ν = ν0 +
1− 2
1− 2 2πT2
ν=±∞ ν = ν0 −
2πT2
D´´0 D´´max D´´min
3 1+ 2
ν = ν0 ± 1+ 2 ν = ν0 +
2πT2 ν = ν0 − 2πT2
2πT2
ν=±∞
ν = ν0
D´´´0 D´´´max D´´´min 5−2 5
ν = ν0 ±
1± 2 ν = ν0 ±
2πT2 2πT2
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Calculating Intensities for First Order Multiplets
28 Calculating Intensities for First

Order Multiplets
A Parts from 1/2AIXn Spin Systems
n magnetically equivalent X-nuclei with spins I ≥ 1/2 form a composite particle IXn and couple to a
single spin of type I = 1/2. A first order multiplet is observed for the NMR spectrum of the A-
nucleus. In order to understand, analyze and simulate those multiplet structures, we will deal with
this problem in three steps.
1/2
Part I Spins A with I = ½ A1/2Xn
1/2 1/2
Intensity rules for the A part of this standard A Xn spin system (conveniently abbreviated as
AXn) may be summed up in the well known Pascal triangle (of the “first kind”). Explicit expressions
are given for the total number of lines (lT), total intensity (intT) and individual intensity (i(n,l)) of each
line in those multiplets. Using
Number of spins in group Xn n n

Total number of lines in A multiplet lT n+1
n
Total intensity of lines in A multiplet intT 2
Intensity of line (n,l) in A multiplet int(n,l) int(n-1,l-1) + int(n-1,l)
and int(n,0) ≡ 0 we obtain the classical Pascal triangle
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Pascal
Line No. l
1 2 3 4 5 6 7
n lT intT int(n,l) - Intensities of A-multiplets
0 1 1 1
1 2 2 1 1
2 3 4 1 2 1
3 4 8 1 3 3 1
4 5 18 1 4 6 4 1
5 6 32 1 5 10 10 5 1
6 7 64 1 6 15 20 15 6 1
The A-multiplets are symmetric with respect to a corresponding center frequency νA. The (n+1)
individual lines resonate at frequencies νl =ν A + mX ⋅ JAX , where mX = n + 1− l and

n n 2
1 ≤ l ≤ n + 1. Hence the separation between two neighboring lines of those multiplets corresponds
to the absolute value of JAX.
n Intensities of A-multiplets
0 1
1 1 1
2 1 2 1
3 1 3 3 1
4 1 4 6 4 1
5 1 5 10 10 5 1
6 1 6 15 20 15 6 1
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Some characteristic multiplets are visualized as shown below:
30 10 -10 -30 30 10 -10 -30
30 10 -10 -30 30 10 -10 -30
30 10 -10 -30 30 10 -10 -30

( Hz)
A Xn systems. n = 1 to 6. νA = 0 Hz. JAX = 10 Hz.

1/2 1/2
Figure 659 : Simulations of A multiplets from
1/2 1/2
Practical examples for typical A Xn systems are shown in the following table
n Examples
13
1 CHCl3 R2PF
13 -
2 CH2Cl2 RPF2 PH2
13
3 CH3Cl PF3 PH3
13 + +
4 CH4 PF4 PH4
5 PF5
-
6 PF6
Remark: A-nucleus, X-nuclei
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Frequencies of A-multiplets
Line No. l
1 2 3 4 5 6 7
n ν(n,l) - Frequencies of A-multiplets
0 νA
1 1
1 νA + ⋅ JAX ν A − ⋅ JAX
2 2
2 ν A + JAX νA ν A − JAX νA
3 1 1 3
3 νA + ⋅ JAX ν A + ⋅ JAX ν A − ⋅ JAX ν A − ⋅ JAX
2 2 2 2
4 ν A + 2 ⋅ JAX ν A + JAX νA ν A − JAX ν A − 2 ⋅ JAX
5 3 1 1 3 5
5 νA + ⋅ JAX ν A + ⋅ JAX ν A + ⋅ JAX ν A − ⋅ JAX ν A − ⋅ JAX ν A − ⋅ JAX
2 2 2 2 2 2
6 ν A + 3 ⋅ JAX ν A + 2 ⋅ JAX ν A + JAX νA ν A − JAX ν A − 2 ⋅ JAX ν A − 3 ⋅ JAX
1/2
Part II Spins X with I = 1 A1Xn
Deuterated compounds give rise to more complex but still first order NMR spectra in practical
examples like:
n
13 -
1 CDCl3 CHDCl3 PHD PH2D
13 - +
2 CD2Cl2 CHD2OD PD2 PHD2 PH2D2
13 +
3 CD3Cl PD3 PHD3
13 +
4 CD4 PD4
Remark: A-nucleus, X-nuclei
Practically important are partially deuterated solvents CHD2OD, CHD2COCD3, CHD2C6D5, etc.
1/2 1 1
which show the familiar A X2 pattern, a “quintet” in H NMR.
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1/2 1
To understand the A part of A X2 systems we can set up a Pascal triangle of “second kind”:
Line No. l
1 2 3 4 5 6 7 8 9
n lT intT int(n,l) - Intensities of A-Multiplets
0 1 1 1
1 3 3 1 1 1
2 5 9 1 2 3 2 1
3 7 27 1 3 6 7 6 3 1
4 9 81 1 4 10 16 19 16 10 4 1
with variables
number of spins in group Xn n n

total number of lines lT 2n+1
n
total intensity of lines intT 3
intensity of line (n,l) int(n,l) int(n-1,l-2) + int(n-1,l-1) + int(n-1,l)
Remark: int(n,<1) ≡ 0, int(n,>n) ≡ 0.
Again the A-multiplets are symmetric with respect to the corresponding center frequency νA. The
(2n+1) individual lines resonate at frequencies νl =ν A + mX ⋅ JAX , where mX = n + 1− l

n n
and 1 ≤ l ≤ 2n + 1 . Hence the separation between two neighboring lines of those multiplets again
corresponds to the absolute value of JAX.
n Intensities of A-Multiplets
0 1
1 1 1 1
2 1 2 3 2 1
3 1 3 6 7 6 3 1
4 1 4 10 16 19 16 10 4 1
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Some characteristic multiplets are visualized as shown below:
45 40 35 30 25 20 15 10 5 0 -5 -10-15-20-25-30-35-40-45
45 40 35 30 25 20 15 10 5 0 -5 -10-15-20-25-30-35-40-45
45 40 35 30 25 20 15 10 5 0 -5 -10-15-20-25-30-35-40-45
45 40 35 30 25 20 15 10 5 0 -5 -10-15-20-25-30-35-40-45
( Hz)
A Xn systems: n = 1 to 4. νA = 0 Hz. JAX = 10 Hz.

1/2 1
Figure 660 : Simulation of A multiplets from
1/2
Part III Spins X with General I AIXn
Kuss and Brehm derived a general formula to calculate efficiently the spectral intensities for the A-
1/2 I
multiplet lines of a general A Xn system and described their findings in a paper entitled:
“Intensitätsformel für Hyperfeinstrukturlinien bei n äquivalenten Kernen mit beliebigem
Spinmoment“. I. E. Kuss and U. Brehm; Org. Magn. Res. 3, 325-330 (1971).
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A Pascal triangle of “higher kind” is set up where the elements in the n-th line and the l-th row are
defined by:
a  n   n+l−k⋅r − 2 
Int(n,l) = ∑ ( −1) ⋅   ⋅ 
k
 k   n−1 
k =0    
l −1
a ≤ max int( ) and ≤ n
r
=r 2 I + 1
• The total number of lines lT = 2nI+1.

•
n
The total intensity in the n-the row corresponds to (2I+1) .
• Each element int(n,l) in the n-the row is calculated by adding up r elements symmetrically
placed above in the (n-1)-th row.
Remark: Implicitly we used those rules to calculate the Pascal triangle for I = ½ and I = 1 shown in
the two previous chapters.
Those higher A-multiplets are symmetric with respect to a corresponding center frequency νA.
The (2n+1) individual lines resonate at frequencies νl =ν A + mX ⋅ JAX , where

n
mX = nI + 1− l and 1 ≤ l ≤ 2nI + 1.
n
Hence the separation between two neighboring lines of those multiplets again corresponds to the
absolute value of JAX.
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1/2 3/2
Some characteristic multiplets are visualized as shown below using the A Xn case with
n = 1 to 4:
80 60 40 20 0 -20 -40 -60 -80
80 60 40 20 0 -20 -40 -60 -80
80 60 40 20 0 -20 -40 -60 -80
80 60 40 20 0 -20 -40 -60 -80

( Hz)
Figure 661 : Figure 3: Simulation of A multiplets from A Xn systems. n = 1 to 4. νA = 0 Hz. JAX = 10

1/2 3/2
Hz.
1/2 3/2
Optional Exercise: Calculate the individual intensities for A Xn cases with n = 1 to 4 using the
general algebraic expressions given by Kuss and Brehm.
2 11 14 51
Applications: NMR spectra with H, and hetero nuclei e.g.: B (I = 3/2), N (I = 3/2), V (I = 7/2),
93 121
Nb (I = 9/2), Sb (I = 5/2) etc.
Remember: TopSpin / DAISY is able to calculate NMR spectra with single spins of I ≥ 1/2 and
composite particles holding spins with I ≥ ½.
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Appendix
Appendix
A.1 List of Compounds in Book I
This manuscript deals with hypothetical and experimental spectral systems. Practical compounds
discussed in specific chapters are listed below.
The A1 System – Spin System No. 1

1
CHCl3 ( H NMR).
19 35 35 37 35 37 37
CFCl3 ( F NMR), isotope shifts, CF Cl3, CF Cl2 Cl, CF Cl Cl2, CF Cl3.
31 13 - 195 2 195
PCl3 ( P NMR), CCl4 ( C NMR), [PtCl6] ( Pt NMR), [PtBr6] ( Pt NMR).
1 1 31
C2HCl3 ( H NMR), C6HCl5 ( H NMR), H3PO4 ( P NMR).
The AX System – Spin System No. 2

Homonuclear AX: 2,3-C4H2Br2S, gem-CH2=CClBr, gem-CF2=CClBr, cis-CFCl=CBrF, trans-
CFCl=CBrlF, CHCl2C(O)H, CHCl2C(OEt)2H,
Heteronuclear AX: CHCl2F, gem-CHF=CCl2, cis-CHCl=CClF¸ trans-CHCl=CClF¸ CHCl2P(O)Cl2,
PCl2F, CH3C(O)N(Ph)CH(Ph)PO3H2. trans-C6H5CH=CFCOOH, cis- and trans-
13 13 15 13 15
CHF=CFP(O)(OCH3)2, Br CH2- COOEt, E- and Z-Boc- NH- CH2-COOH, Boc2 NH, protolytic
13 15 13 15 -
equilibrium of H C N - C N
The AB System – Spin System No. 3

2,4-C4H2Br2S, CH2ClCCl(Ph)COOH, CHCl(Ph)CHClCOOH, sterically hindered ethanes
CHBr(C6H5)CHBrC(O)C6H5, CHBr(C6H5)CHBrC(O)OC2H5, cis-c-C3H2(CH3)2(OSi(CH3)3)2
H H
C C
N S
C
Nuclear specific spectral half width from

Br
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Appendix
The A2 System – Spin System No. 4

1,2,3,4-C6H2Cl4, 1,2,4,5- C6H2Cl4, cis and trans CHCl=CHCl and HOOCH=HCOOH,
35 35 37 37
CH2Cl2, CF2Cl2, isotopomers CF2 Cl2, CF2 Cl Cl, and CF2 Cl2, CCl2=CH-CH=CCl2, CHCl=CCl-
CCl=CHCl, trans-c-C3H2(CH3)2(OSi(CH3)3)2.
The AMX System – Spin System No. 5

13
Heteronuclear: CHCl2F, 1,3,5-C6H3ClBrJ, CH2BrCHBrCOOH, CH2=CHCN, CF2=CFCl,
Homonuclear: 2-C4H3COOH, CHClFP(O)Cl2,
Mixed nuclear: C6H2C3lF, CH2=CBr-P(O)(OR)2, cis- and trans-CHBr=CH-P(O)(OR)2.
The ABX System – Spin System No. 6

Homonuclear ABX Systems: CH2-CH fragments: HOOC-CH2-CH(SO3H)-COOH, HOOC-CH2-
CH(OH)COOH. CF2-CF fragments: c- C3Cl3F3, c-C4Cl5F3.
+ -
Heteronuclear ABX systems: [NH4] [CH2=CF-COO] , CHF2P(Ph)(O)OEt, CHBr=CF2, cis- and
trans-CHF=CBrF, C2H2Cl3F, CH2=CClPCl2, H2O3PCH=CHPO3H2,
The AXX´ System – Spin System No. 7

Isotopomers of: cis- and trans CHCl=CHCl, 1,2,3,4-C6H2Cl4, 1,2,3,5-C6H2Cl4, and 1,2,4,5-C6H2Cl4,
(CH3O)2(O)PCH2P(O)(OCH3)2, (CH3O)2(O)P CH2CH2P(O)(OCH3)2,
NMR-titration of H2O3P-CH2CH2-PO3H2.
The AX2 System – Spin System No. 8

5-
Homonuclear A2X and AX2 systems: CH2Cl-CHCl2, CF2Cl-CFCl2, ClF3, RSF3, [P3O10] .
Heteronuclear A2X systems: CH2ClF, CH2ClPCl2, C6H2Cl3F,
The ABC System – Spin System No. 9

Ethane derivates: tBu-CHX-CH2X (X = Cl, Br), CH2X-CHY-COOH (X, Y = halogens)
Ethylene derivatives: CH2=CHCN, CH2=CHC6H5, NMR-Titration of CH2=CHCOOH, CH2=CHPO3H2.
Benzene derivatives: 1,2,4-C6H3Cl3, 1,3,5-C6H3Cl,BrJ.
Heterocyclic derivatives: Thiophenes 2-C4H3SCl, 3-C4H3SCl, 2-C4H3SBr, 3-C4H3SBr.
The ABB´ and the AA´B System – Spin System No. 10

CH2=CHCOOH at pH, 4.55, CH2Br-CHDBr
The AB2 System – Spin System No. 11

2,6-(CH3)2C6H3OH, 2,6-C6H3NCl2, 2,6-(CH3O)2C6H3N, 1,2,3-C6H3Cl3, [CH3P]3,
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Appendix
The AAÁ´´, AA´2, and A3 Systems – Spin System No. 12, 13, 14
1,3,5- C6H3Cl3, CH3Cl, CH3COOR, RCOOCH3, RCOCH3, ROCH3, CH3COOCH3 Ar-CH3
35 37
CF3Cl, isotopomers CF3 Cl and CF3 Cl.
The AMRX System – Spin System No. 15
H4 H4
H
H H F
H5 H3 H5 H3 H
C C
C C
C C H
H O C C C
H6 N O H6 N O H S O
O
CH3 CH3
13
Threo- and erythro-CFClBr-CFBr-CF=CFBr, CHClFPCl2, CH2=CHOP(O)(OCH3)2,
2 isomers of C6H2F2ClCOOH: 2-chloro-4,5-difluorobenzoic acid and 4-chloro-2,5-difluoro-benzoic
2+
acid CF2=CFPCl2, tris(bipyridyl)ruthenium(II) cation [Ru(bip)3] .
The ABMX and Related AMNX, AMXY Systems – Spin System No. 16
5-fluoro-3-thiolene-2-one, CHF(Ph)-CH2COOEt, CH2(Ph)-CHFCOOEt.
The A2MX and Related AM2X, AMX2 Systems – Spin System No. 18
Homonuclear: ∆ - and ∆ -pyrrolidine-2-one.

3 4
Heteronuclear: 2 isomers of C6H2Cl2F2, CHF2PCl2, CCl2=CH-CH2-P(O)(OEt)2.
The ABXY System – Spin System No. 19

1 31
-CH2-CH2- fragment of 2-methoxy-1-oxa-3-thia-phospholane. H{ P} NMR.
-CH2-CH2- fragment of (CH3)(Cl)(O)P-CH2-CH2-C(O)Cl, 2-(P-methyl-P-chloro-phosphinyl)-
propionylchloride. 1H{31P} NMR. Isomers of C6H2F2ClBr.
The ABCX System – Spin System No. 20

1 2 1 2 1 2
Aliphatic compounds: CR H2-CR HC(O)H, CR H2-CR HF, CR H2-CR HP* (P* = P(O)Cl2,
P(O)(OR)2).
Cyclo-aliphatic compounds: trans-1,2-R2-C3H3F, trans-1,2-R2-C3H3P*.
Olefinic compounds: CH2=CHC(O)H, CH2=CHC(O)F, CH2=CHF, CH2=CHP* (P* = P(O)Cl2,
P(O)(OR)2,), NMR Titration of CH2=CH-PO3H2.
1 2
Aromatic compounds: isomers of C6H3FR R .
Heterocyclic compounds: isomers of C5NH3F.
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Appendix
The ABX2 System – Spin System No. 23

trans-CHCl=CH-CH2Cl, c-C3F4Cl2.
The A2BX and the AB2X System – Spin System No. 24

1-fluoro-2,6-dichlorobenzene 1,2,6-C6H3FCl2, CH2C=C=CHPR2, CH2C=C=CHP(O)R2.
The [AX]2 System – Spin System No. 27

Heteronuclear: CH2=CF2, cis- and trans-CHF=CHF, isomers of C6H2F2R2.
Homonuclear: p-C6H4FCOOH, (1H{19F} NMR), o-C6F4Br2, γ-Pyrone, [PcHex]4[Cr(CO)5]2 ( P{ H}

31 1
15 15 13 13
NMR), cis- and trans- F N= FF, F(O) C- C(O)F.
The A2X2 System – Spin System No. 30

Homonuclear systems: c-C3H4, c-C3F4,
4- 4-
Heteronuclear systems: CH2F2, CH2=C=CF2, [O3P-CH2-PO3] , [O3P-CF2-PO3] .
The AX3 System – Spin System No. 31

Homonuclear systems: CH3CHO, CH3CH(OH)OCH3, CH3CH(OCH3)2, CH3CH(OH)2,
CH3-CHCl2, CH3-CCl2-CHCl2 etc..
Heteronuclear systems: CF3H, CF3-CHR2, CF3-C ≡ CH, PH , PF , CH P(E)R , CF P(E)R , Cl-Au-
3 3 3 2 3 2
PF3.
The ABCD System – Spin System No. 32

1 2 1 2
o-C6H4R R , o-C6H4ClBr, o-C6H4(COOH)SO3Na, o-C6H4(COOH)NH2, m-C6H4R R , m-C6H4ClBr,
N-methyl-pyridone, cis- and trans-CHCl=CH-CCl=CH2, Asymmetrically substituted cyclobutanes c-
1 2
C4H4R 2R 2.
The ABC2 and Related AB2C, A2BC Systems – Spin System No. 34
m-C6H4R2, trans-CHCl=CH-CH2Cl
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Appendix
The [AB]2 System Part 1: o-Disubstituted Benzenes – Spin System No. 37

1 2 1 2 1 2 1 2
o-C6H4R2, p-C6H4R R , CH2R -CH2R , c-C2H4SO3, c-C3H4R R , c-C4H4R 2R 2, cis- and trans-
CHCl=CH-CH=CHCl, CH2=CCl-CCl=CH2.
Four classes of [AB]2:
1: N ≥ K ≥ M ≥ L . 2: N ≈ L > K >> M . 3: K >> N >> L ≈ M . 4: L ≈ K >> M ≈ N

Class 1
HB
HA HX
Fe(CO)3
HA HX
HB 1 1
( H{ H}),
o-C6H4R2: o-C6H4Cl2, o-C6H4Br2, I, NO2, tBu.
Steric strain in benzocycloalkane derivates:
H1 H1 H1
H2 H2 H2 CH2
CH2
CH2 CH2
CH2
H3 H3 H3 CH2
H4 H4 H4
H1 H1 O H1 O
H2 O H2 C H2 C
C CH2
CH2
C CH2
H3 O H3 C H3 C
H4 H4 O H4 O
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Appendix
1 19 1 31
7,7-Difluoro-benzo-cyclo-propene ( H{ F}), o-Phenylenechlorodite ( H{ P} NMR)
H1
H1
H2 C
F5 H2 O
C C
P Cl
C C
F6 H3 O
H3 C
H4
H4
Ortho-Polyphenylenes: ortho-tetraphenylene, ortho-hexaphenylene - atropisomer 1
The [AB]2 System Part 2: p-Disubstituted Benzenes – Spin System No. 37
Class 2: N ≈ L > K >> M asymmetrically disubstituted para-benzene derivatives
p-C6H4R R (R = Halogen, R = Halogen, OMe, NO2, COOH, R ≠ R ).

1 2 1 2 1 2
The [AB]2 System Part 3: Ethane Fragments HFP – Spin System No. 37
Class 3: K >> N >> L ≈ M

rotating 1,2-disubstituted ethanes:
Br-CH2-CH2-Cl and further R -CH2-CH2-R (R , R = F, Cl, Br, I and other substituents, R ≠ R ).
1 2 1 2 1 2
Bulky substituents: tBu-CH2-CH2-X: (X = F, Cl, Br, J, Li).

-CH2-CH2- in rigid ring systems: 2,2-dibromocyclobutanone, meta-cyclophane
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Appendix
H
O H H4
H Br H H3
H
H Br H H2
H H1
1 2 1 2
Chiral R and R in R -CH2-CH2-R :
1 31
meso and racem forms of (iPrO)(Ph)(O)P-CH2-CH2-P(O)(Ph)(OiPr) ( H{ P} NMR)
Meso Racem
Rigid Skeleton -CF2-CF2- in Substituted Perfluoro Cylobutenes

R = Br, I; R = Cl, Br, I; R ≠ R .
1 2 1 2 1 2
R -CF2-CF2-R
1 2
-CF2-CF2- in substituted perfluoro cylobutenes, e. g. R = Br and R = Cl.
F
R1
C C
F
F
C C
F R1
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Appendix
The [AB]2 System Part 3: Ethane Fragments HFP – Spin System No. 37
P* P*
H C C H
P* P*
P* = P(Ph)(O)OiPr
The [AB]2 System Part 4: Dioxolanes – Spin System No. 37
Class 4: L ≈ K >> M ≈ N Dioxolanes and related cyclic structures
H H H
C O R! C O C O Cl
H H H
H C H S H P
C O 2 C O C O
R O O
H H H
1 31
Ethylenesulphite, 2-oxo-2-chloro-1,3-dioxa-2-phopholane ( H{ P}).
The [AB]2 System Part 5: Final Remarks – Spin System No. 37

o-C6F4Br2: [AX]2 - a limiting case of the [AB]2 system
1 2 1 2
Cyclobutanes [-CHR -CHR -]2: R = COOH, CON(CH3)2. R = C6H5.
Butadienes: CH2=CCl-CCl=CH2, CHCl=CH-CH=CHCl, MeOOC-CH=CH-CH=CH-COOMe.
19 1
CFCl=CF-CF=CFCl. CF2=CH-CH=CF2 ( F{ H} NMR).
Heterocyclic compounds: thiophene, 4-methoxypyridine, N-methyl-4-pyridone.
OCH3 O
H H H H H H
C C
C C
H S H H N H H N H
CH3
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Appendix
The A2B2 System – Spin System No. 40
R H R
C C P P
H R R
H R´ R Cr(CO)5
C C P P
R´ H Cr(CO)5 R
1 31 1
R = C6H5. R´= COOH. ( H NMR) R = c-C6H11 ( P{ H} NMR)
The AB3 Spectrum and the Related A3B Case – Spin System No. 41
CH3OH (AB3), CH3SH (A3B), cis- and trans-isomers of CFCl=CCl-CF3 (AB3 and A3B)
P4O6[Ni(CO)3] and P4O6[Ni(CO)3]3 (AB3 and A3B).
The A4 and Related Spin Systems No. 42 to No. 47

Practically relevant are:
4_Spins_47_A4: CH4, CF4, P4O6, P4O6[Ni(CO)3]4.
4_Spins_44_[[A]2]2: p-C6H4Cl2, CH2Br-CH2Br, C2H4, C2F4.
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Appendix
A.2 List of Compounds in Book 2
This manuscript deals with hypothetical and experimental spectral systems. Practical compounds
discussed in specific chapters are listed below.

1 13 15 129 + -
AHMRX: [ H C N Xe] [AsF6] , [Cr(CO)5*(C6H5P)5], CH2=CCl-CH=CH2.

2 2 2
An, AXn, AnXn, ABn, AnBm, ABXn, A2B2X, ABCXn, ABCDn. JHH, JDH, JTH.
Composite Particles AB4 and A4B

AB4: SF5R. [AB4]2: S2F10.
Composite Particles A2B3 – A2X3 and A3B2 – A3X2 – Analysis of A2B3 Spectra
2+ 2+ 2+ 2+
A2B3, A3B2: [NiL5] , [PdL5] . A2B3X, A3B2X: [RhL5] , [PtL5] . L = P(OR)3.
Five Spins: CH3CH2R – A2B3, A2M3, ABC3, ABM3 Systems

A2B3, A2M3: CH3CH2R. ABC3, ABM3: Nonequivalence in (CH3CH2)2CHR, (CH3CH2)2CRR´. Chirality
in CH3CH2R*. A2B3X, A2M3X: CH3CH2X. ABC3X, ABM3X: (CH3CH2O)2CRR´, (CH3CH2O)nP(Y)Z3-n.
ABC3: CHCl2-CHCl-CH3. A[BC]2: CH2Cl-CHCl-CH2Cl. ABCD3: CH2Cl-CHCl-CH3.

A2B2C3, [AB]2C3: CH3CH2CH2R. [AB]2C3X: CH3CH2CH2CHO, . CH3CH2CH2P(O)Cl2, CH3CH2CH2F.
AB6: (CH3)2CHSiCl3. A6B: (CH3)2CHSi(CH3)3. AB6X: (CH3)2CHP(O)Cl2.
Complex: CH3CH2CH2CH2R, CH3CH2CH(CH3)R, (CH3)2CHCH2R, primitive: (CH3)3CR.
Complex: [ABC]2D3X: CH3CH2CH2CH2P(O)Cl2. ABCD3E3X: CH3CH2CH(CH3)P(O)Cl2, A2BC6X:
(CH3)2CHCH2P(O)Cl2, primitive: A9X: (CH3)3CP(O)Cl2.
Five to Six Spins: H-F-Aliphatic Compounds

ABCXY: CH2FCHFCOOEt. Series C2HnF5-nCOOEt. A6,X6, A2B3X,AM3X2, AM3X,A2M3X, [[A]2X]2,
[A[X]2]2. A3X3, A[MR]2X in fluoroethanes C2HnF6-n and fluoroacetones: C3HnOF6-n.
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Appendix

ABCD3, ABC3, ABCX3, ABX3: CH3CH=CH2, CH3CH=CHCl, CH3CCl=CH2. ABCD2X, ABCDX2,
ABCX3, ABCM2X, ABCMX2, ABCX3: CH2FCH=CH2, CHF2CH=CH2, CF3CH=CH2. ABC3, ABX3,
AMX3: CF3CCl=CF2. AMNR3: CF3CF=CF2.

ABC3 to ABX3 : trans- and cis-CH3CH=CHCOOR. Fragmentation. Deconvolution.

AMNCX, AMRXY, AHMRX: allyl glycidyl ether, CH2=CH-CH2-O-CH2-CH(O)CH2. Fragmentation.
Iterating two separate 5-spin systems or one 10-spin system.
Five to Six Spins: ABCDE and ABCDEX – Butadienes

ABCDE: Methoxybutadienes CH(OCH3)=CH-CH=CH2, CH2=C(OCH3)-CH=CH2. ABCDE- and
1 19 1 19
ABCDEX: CH2=CF-CH=CH2. H{ F}, H and F NMR. [ABC]2: CH2=CH-CH=CH2. [AMX]2:
CF2=CF-CF=CF2.
Five to Seven Spins – Cyclopropanes

[AB]2C: c-C3H5R, mono-substituted cyclopropanes. ABCD3: CH2(O)CH-CH3, propylene oxide.
ABCDE: CH2(O)CH-CH2R, epichlorohydrine etc. ABCDEX: CH2(O)CH-CH2R, epifluorohydrine.
[ABC]2 : CH2(O)CH-CH(O)CH2, dioxidobutane.
Cyclobutanes: ABCDE at Lower Fields, AHKRX at Higher Fields

ABCDE to AHKRX: C4Cl3F5, 1,1,2-trichloro-2,3,3,4,4-pentafluoro-cyclobutane. [ABC]2 to [AMX]2:
C4Cl2F6, C4Br2F6. ABCDEX - AHKRTX: C4HBr2F5 in 1,2-dibromo-2,3,3,4,4-pentafluorocyclobutane.
A[BC]2DE: C4H7CN, cyanocyclobutane at 800 MHz.

[A[B]2]2, [A[X]2]2, [X[Y]2]2, AX[YZ]2, X[YZ]2, A[XY]2, [XY]2, [[X]2]2, [A6[M]2X]2: 1,2-di-substituted
3,3,4,4-tetrafluorocyclobutenes and related structures.
[[A]2X]2, [AMX]2, [AMX]2B, [A[B]2C]2: 1,2-disubstituted 3,3,4,4,5,5-hexafluorocyclopen-tenes and
related structures.
Five to Six Spins – Phenyl Groups in C6H5R

[AB]2C, [AC]2B, [BA]2C, [CA]2B: C6H5R. Substituent effects on spectral patterns, chemical shifts,
3 4 5
coupling constants JHH (ortho), JHH (meta), JHH (para). [AC]2BX, [CA]2BX, [AB]2CX, [AC]2BX3,
15
[AB]2C +XYZ or [AB]2CXYZ, 2 [AB]2C or [[AB]2C]2: C6H5R (R = CHO, F, N, CH3, CH=CH2, C6H5).
n
Long range couplings JHH. A6: C6H6. Detection of hidden couplings. [AB]2C+[DE]2F:
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Appendix
1 13 1
C6H5COOC6H5. H/ C{ H}. Fragmentation, spin assignment by HHCOSY, HSQC, iteration. [AC]2B
and ABCD: C6H5-C5H4N, 2-benzoylpyridine.
19
F NMR Spectra of Pentafluorophenyl Groups in C6F5R Compounds
[AC]2B, [AB]2C: C6F5R. Substituent effects on spectral patterns, chemical shifts, coupling constants
3 4 5
JFF (ortho), JFF (meta), JFF (para). [AC]2BX: C6H5F. [AC]2CX3: C6F5CF3. [AC]2CX9: R = Si(CH3)3.
n n
Long range couplings JFH. [[AC]2B]n: (C6F5)nSiBr4-n. Long range couplings JFF. Through space
19
couplings. ABCDE: C6F5 group in C6F5SF3, disturbing the symmetry at low temperature F NMR.

A6, [AB]2CX, [ABX]2, A[BX]2C, [[A]2X]2, [AX]2BY, ABCXYZ, [AX]3, [A[X]2]2, [AX]2YZ, [AXY]2, A[XY]2Z,
X6: 13 compounds of type C6H6-nFn (n = 0 to 6). Stereo specific chemical shifts δH, δF, and coupling
n n n
constants JHH, JFH, JFF (n = 3-5).

19 1
First order ( F) and second order ( H) homonuclear 7-spin systems in chinolines. Second order
1
( H) homonuclear 6-spin system in cationic, neutral and anionic forms of 8-hydroxy-quinoline

[AB]4 (D2h): 8-spin case, naphthalene. [ABCD]2X: 9-spin case, thioxanthene carbanion, simplified
1
to ABCDX for ABCD part. [ABCDX]2 expected, but ABCD (8 H) and X2 found: H NMR of
phenanthrene C14H10. Simple spectra from substituted phenanthrenes. 12 spin system from 3,4-
1
Dibenzoperylene, fragmented to simple A1, AX, AMX, AMXY, and AMRX approximations in H
NMR spectrum.

The [AXn]2 system. "Harris-Multiplets". A and X parts. Systems with long range coupling JXX´ = 0
and JXX´ ≠ 0. More complex problems: [AMmXn]2, [AXn]3, [AXn]4. Phosphorous, fluorine- and
- -
coordination-chemistry. Final examples: [V(PF3)6] and [Nb(PF3)6] .
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Appendix
A.3 Suggested Readings
More about theory or experimental techniques in NMR spectral analysis will be found in several
books and in papers quoted in specific chapters of this manuscript. Valuable information is also
available from the Bruker NMR Guide collection.
Books
J. H. Nelson; "Nuclear Magnetic Resonance Spectroscopy". Prentice Hall, Upper Saddle River,
2003. ISBN 0-13-033451-0.
J. W. Akitt and B. E. Mann; "NMR and Chemistry - An introduction to modern NMR spectroscopy".
Stanley Thornes, Cheltenham, 2000. ISBN 0 7487 4344 8.
U. Weber and H. Thiele; "NMR Spectroscopy: Modern Spectral Analysis". Wiley-VCH, Weinheim,
1998. ISBN 3-527-28828-7.
(This book is particularly recommended. It combines NMR Spectral Analysis and Applications of
DAISY, a Bruker program for Automated Analysis and Simulation of 1D NMR Spectra).
H. Friebolin; "Ein- und zweidimensionale NMR-Spektroskopie". VCH, Weinheim, 1992. ISBN 3-

527-28507-5.
A. Derome; "Modern NMR Techniques for Chemistry Research". Pergamon Press, Oxford, 1987.
ISBN 0-08-032513-0.
R. K. Harris; "Nuclear Magnetic Resonance Spectroscopy". Pittmann, London, 1983. ISBN 0-273-
01684-9.
H. Günther; "NMR Spectroscopy". John Wiley & Sons, Chichester, 1980. ISBN 0-471-27579-4.
R. J. Abraham; "Analysis of High Resolution NMR Spectra". Elsevier, Amsterdam, 1971. ISBN 0-
444-40846-0.
P. L. Corio; "Structure of High-Resolution NMR Spectra". Academic Press, New York, 1966. ISBN
0-13-033451-0.
H146197_00_01
913
Appendix
Bruker NMR Guide
The following links to the NMR-Guide web pages are accessible once the NMR-Guide has been
opened from the TopSpin help system.
Look up your TopSpin and find useful information on a series of topics:
a) Basic principles of 1D NMR (Spins, Hamilton OP, Hamilton Matrix, Eigenwerte, Transitions,
Frequencies, Intensities, Relaxation) are covered by Beginner Guides (beginner.pdf) and
Avance 1D and 2D Course (avance_usrmnl3.pdf).
b) NMR programs. A general introduction to TopSpin is integrated in your software TopSpin
(Version: 3.2 pl1 (of October 20 2012)), Bruker BioSpin, Rheinstetten: <topspinhome-
directory>\prog\docu\english\xwinproc\pdf. Link to Principles of NMR:
http://localhost:6600/gui/gethelp.gui?arg=resonance&rnd=-4589160375486537496
c) An extended Introduction covers the following subjects: Angular momentum and nuclear
magnetism, Larmor Frequency, Bloch Equations, Nuclear spin and resonance, the vector
model, A pulse, Evolution of chemical shift and coupling constant, line width, spin-echo, time-
domain, frequency-domain. See:
http://localhost:6600/guide/eNMR/NMRnotes/nmr/nmr.html
d) Topics of Signal selection, Phase cycle, exorcycle, cyclops, gradient selection, coherence
transfer pathway, are described under:
http://localhost:6600/guide/eNMR/NMRnotes/nmr/nmr.html
e) The second dimension handles: Lineshapes, quadrature detection, magnitude mode, phase
sensitive, axial peaks. See:
http://localhost:6600/guide/eNMR/utilities/standard.html
Comments on References are given by:
http://localhost:6600/guide/eNMR/eNMRindex.html
http://localhost:6600/guide/eNMR/appli.html
http://localhost:6600/guide/eNMR/chem/NMRnuclei.html
http://localhost:6600/guide/eNMR/chem/H.html
And finally, the Periodic Table of elements including spin active isotopes is found under:
http://localhost:6600/guide/eNMR/chem/introperiod.html
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914
Appendix
H146197_00_01
915

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TopSpin

Analysis of 1D NMR Spectra

A Practical Approach to Simple and

All rights reserved. No part of this publication may be reproduced, stored

This manual was written by

© January 17, 2017 Bruker Corporation

For further technical assistance please do not hesitate to contact your

Bruker BioSpin GmbH

Phone: + 49 721 5161 6155

1 Summary of Contents .................................................................................. 3

5 One-Spin System ....................................................................................... 39

6 Two-Spin Systems ..................................................................................... 57

7 Three-Spin Systems ................................................................................. 101

8 Four-Spin Systems .................................................................................. 257

Book 2 ............................................................................................................... 583

9 First Order Systems from Single Spins ................................................. 585

10 The Composite Particle Concept ............................................................ 589

12 Seven and More Spins: C3 to C5 Alkyl Groups ..................................... 653

13 Five to Six Spins: H-F-Aliphatic Compounds ........................................ 681

14 Five to Six Spins: Propene and Halopropenes .......................................687

15 Five Spins: ABC3 to ABX3 Crotonic Acid Ethylester ..............................695

17 Five to Six Spins: ABCDE and ABCDEX – Butadienes ..........................711

18 Five to Seven Spins: Cycloalkanes .........................................................723

19 Four to Eight Spins: Cycloalkenes ..........................................................745

20 Five to Six Spins: Phenyl and Pentafluorophenyl Groups ....................751

21 Six Spins in C6H6-nFn .................................................................................807

22 Seven Spins: Quinolines ..........................................................................811

23 Seven to Twelve Spins: Polycyclic Aromatic Ring Compounds ..........819

24 Practical Examples from Multi-Spin Systems with Symmetry ..............831

25 Samples, Solvents, Temperature .............................................................851

26 Number of Transitions for Coupled Systems of Spins I = ½. ................883

27 Lorentzian Line Shape of a Singlet..........................................................885

28 Calculating Intensities for First Order Multiplets ...................................891

1 Summary of Contents .................................................................................. 3

4.1 Some Introductory Remarks .................................................................................19

4.2 Developing the 47 Characteristic One- to Four-Spin Systems.............................33

5 One-Spin System ....................................................................................... 39

5.1 The A1 System – Spin System No. 1 ....................................................................39

5.2 Some Comments on Lorentzian Line Shapes of Resonance Signals..................42

5.2.1 The Lorentzian Singlet Absorption Signal Centered at ν0 ....................................43

5.2.2 The Lorentzian Singlet Dispersion Signal Centered at ν0 ....................................44

5.2.3 Integration of a Lorentzian Singlet Absorption Line..............................................45

5.5 The Isotope Effect on Resonance Frequencies / Chemical Shifts .......................48

5.6 Lorentzian Absorption Spectra from Superimposing Singlet Lines ......................54

5.7 Practical Examples for 1-Spin Spectra .................................................................56

6 Two-Spin Systems ..................................................................................... 57

6.1 The AX System – Spin System No. 2 ...................................................................57

6.1.2 Some Examples for Homonuclear AX Spin Systems ...........................................70

6.1.3 A Heteronuclear AX Spin System with Rotational Isomerism ............................. 71

6.1.5 CHF=CHP(O)(OCH3)2 – a Heteronuclear RX System ......................................... 82

6.2 The AB System – Spin System No. 3 .................................................................. 85

6.2.1 2,3-Dibromothiophene – a Typical Example for AB Spectra ............................... 89

6.2.2 Geometrical Solution of the AB Problem ............................................................. 90

6.2.3 Further Practical Examples of AB Systems are Shown Below ............................ 91

6.2.4 Sterically Hindered Ethanes CHRBr-CHR´Br ...................................................... 92

6.2.6 AB Spectra with Nucleus Specific Half Widths .................................................... 95

6.3 The A2 System – Spin System No. 4 ................................................................... 97

7 Three-Spin Systems .................................................................................101

7.1 The AMX System – Spin System No. 5 ............................................................. 102

7.1.1 Practical Examples ............................................................................................ 104

7.1.3 Some Complications with Homonuclear AMX Spectra ..................................... 109

7.1.5 Double Resonance Experiments and Simulations ............................................ 122

7.2 The ABX System – Spin System No. 6 ............................................................. 132