Nuclear Magnetic Resonance (NMR) Spectroscopy

basic theory 1. properties of nucleus spin of nucleus nuclear spin quantum number I = n/2 n : integer atomic mass number number Z A I example 1 12C, 16O, 28Si, 56Fe even even 0 odd even n : even 2H, 10B, 14N, 50V odd odd n : odd 1H, 13C, 19F, 55Mn * NMR properties of some nuclei with I = 1/2 * NMR properties of some quadrupolar nuclei (I > 1/2) number of possible spin states = 2I + 1 magnetic quantum number m = +I, +(I-1), ., -I without a magnetic field, the spin states are degenerate nucleus I No. of states m values 1 1H 1/2 2 +1/2, -1/2 11B 3/2 4 +3/2, +1/2, -1/2, -3/2 1 12C 0 1 0 14N 1 3 +1, 0, -1 1

NMR properties of some nuclei with I = 1/2

NMR properties of some quadrupolar nuclei (I > 1/2)

2. nuclear Zeeman effect a nucleus with I0 in a magnetic field, 2I+1 spin states are not degenerate; they separate in energy with the largest positive m value corresponding to the lowest-energy state ex. I = 1/2 m = -1/2

Bo

DE
m = +1/2 Bo

spin state energy gh Ei = -miBo g : magnetogyric ratio 2p transition Dm = -1 for a nucleus with I = 1/2, the energy difference g h Bo DE = 2p precession some sort of uniform periodic motion, the magnetic moment wobble around the axis of applied field Lamar frequency w = gBo linear Lamar frequency u = w/2p = gBo/2p 4

Boltzmann distribution Pm=-1/2 ghBo D E/kT = e DE = Pm=+1/2 2p If Bo = 2.35 T DE = 6.63 x 10-26 J Pm= -1/2 Pm=-1/2 =0.4999959 = 0.999984 Pm= +1/2 Pm=+1/2 =0.5000041 experimental considerations sample solution solid (magic-angle spin) magnet radio-frequency transmitter spectrometer receiver decoupler recording device

magnet : permanent magnet (1 2 T) electromagnet (1.8 2.3 T) superconducting magnet (up to 13 T) two important characteristics of magnet stability sensitive to temperature homogeneity continuous wave experiment 1. frequency-sweep

2. field-sweep

Fourier transform technique

relaxation processes spin-lattice relaxation T1

Peq P = (Peq Po) e -t/T1

spin-spin relaxation T2 much faster than spin-lattice relaxation T2 < T1

information from NMR spectrum (1) chemical shift the nuclei are screen from the magnetic field Bo, the net field effective at a nucleus is Beff = Bo (1 s) s : the shielding constant each chemically distinct nucleus is associated with a characteristic frequency ex. B10H14 4 distinct B nuclei

chemical shift d relative to a standard for the isotope concerned uobs - uref 6 d = 10
spectrometer frequency

unit: ppm a shift to higher frequency than standard ==> positive d

decrease in shielding increase in chemical shift
8

relative NMR frequency (MHz) standard nucleus (B0 = 4.7 T) reference 1H 200.0 (CH3)4Si 13C 50.2 (CH3)4Si 19F 188.2 CFCl3 29Si 39.8 (CH3)4Si 31P 81.0 85% aq. H3PO4 77Se 38.2 (CH3)2Se 119Sn 74.5 (CH3)4Sn 195Pt 43.0 [Pt(CN)6]2-

compound common range (ppm) 1

-30 20 -100 400 -200 200 -350 40 -100 250 -300 200 -1000 8000 -200 15000

(2) intensity integration of the area not for 13C (3) spin-spin coupling non-equivalent magnetically active nuclei couple each other chemically equivalent magnetically equivalent

notation

Dd >> J Dd small

A, X, M, Q A, B, C

splitting pattern 2nI + 1 coupling constant J ex. 1H, 13C NMR spectra of H13CO2-

(i) first-order (ii) satellites (iii) second-order

(4) exchange
10

11

number of lines splitting determined by Pascals triangle

number of equivalent name of coupling nuclei pattern ratio of integration
1

0 1 2 3 4 5

singlet doublet triplet quartet quintet sextet

1
1 1 1 1 5 3 4 2

1
1 3 6 4 5 1 1 1
12

10 10

AX2 ?? classification of the nuclei I = 1/2, 100%abundance 1H, 31P, 19F, 103Rh I = 1/2, low abundance
13C, 15N, 29Si, 77Se, 109Ag, 119Sn, 125Te, 183W, 195Pt, 199Hg

I > 1/2, 100% abundance 14N, 27Al, 51V, 59Co

I > 1/2, low abundance (I) 1H

11B, 121Sb, 193Ir

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14

Sn(CH3)4 1H

119Sn

52 Hz

54 Hz

expanded 1H
Hz

13C
1J119 Sn-13C =

329

1J117

Sn-13C =

317

Hz

15

GeH4

Si2H6

(29Si I = , 4.7%)

16

CH3CH2SPF2

K[BH4]

17

1H

NMR spectrum of PF215NHSiH3

3J

PH

= 8 Hz, 3JHH = 4 Hz, 2JNH = 2 Hz, 4JFH = 2 Hz

1H{15N}

NMR spectrum of PF215NHSiH3

18

[HV(CO)5]2-

doublet of doublet of triplet

J Pt-H = ?

J Pc-H = ?
19

for CH3 (or C(CH3)3) group in tertiary phosphine complexes, doublet 1H spectra indicate mutually cis arrangements and triplet spectra mutually trans
PMe2Ph

PtCl2(PMe2Ph)2

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21

22

23

MCl3xH2O (M: Rh, Ir) (L: PR3, AsR3) (i) Ir, PEt2Ph

KH

MCl3L3 D

EtOH, 1h

MHCl2L3 (I)

MHCl2L3 (II)

158 Hz 19 Hz

18 Hz

12 Hz

24

(ii) Rh, AsMePh2

4 Hz

9 Hz

25

(iii) Rh, PMePh2

206 Hz
2J 1J

HP =

9 Hz RhH = 4 Hz

2J 1J

HP =

14.5, 9 Hz RhH = 13.5 Hz

26

(II) 13C
M-CO

M=C

27

1J

= 35 Hz 2J Pt-C = 0 Hz
Pt-C 1J

= 1936 Hz 2J Pt-C = 180 Hz

Pt-C

28

DEPT

29

20 lines

5 lines

[Ti(13CO)6]213C

47,49

Ti

30

(III) 31P

31

31P

NMR spectrum of P(OMe)3

31P

NMR spectrum of [Cu(PMe)3]+

31P

NMR spectrum of PHF2(15NH2)2

32

31P

NMR spectra of the mixed products from the reaction of trans-[PtCl4(PEt3)2] + trans-[PtBr4(PEt3)2]

[PxFy]-

x=? y=?

33

(IV) 19F

19F

NMR spectrum of the products from the reaction: UF6 + Me3SiCl (halogen exchange)

34

(V) 29Si 29Si NMR spectrum of SiMe 4

(VI) 195Pt

35

2-D NMR 1. correlated spectroscopy (COSY) provide information about couplings between nuclei of a single isotopes the off-diagonal peak at a frequency (f1, f2) implies that there is a coupling between the nuclei resonating at f1 and f2 ex. COSY 11B spectrum for B10H14

B(2), B(4) (-35 ppm) B(6), B(9) (11 ppm) B(1), B(3) (13 ppm) B(5), B(7), B(8), B(10) (1 ppm)

36

ex. COSY 11B spectrum for B9H11NH

2. heteronuclear correlation spectroscopy (HETCOR or HCOR) ex. HETCOR 11B/1H spectra for B10H14

37

3. nuclear Overhauser effect spectroscopy (NOSEY) identify a NOE which arises from the proximity of the two nuclei in space heteronuclear NOSEY (HOSEY) ex. 2D 1H/6Li HOSEY spectrum for tmeda adduct of 2-lithio-1-phenylpyrrole

38

ex. homonuclear 2D 13C scalar coupling (COSY) and chemical exchange (NOSEY) spectra for [Os3H2(CO)10]

ex.
O=P

CH2CH2Br OCH2CH2 OCH2CH2

expanded 1H NMR spectra

39

COSY (1H1H)

COSY (1H13C)

40

exchange reactions ex. 1 31P{1H} NMR spectrum of the products derived from [Rh4(CO)9{P(OPh)3}3] under 400 atm of CO at 300 K

Rh4 cluster broke down to 2 dinuclear complexes

41

ex. 2

19F

NMR at 180 K chemical shift pattern intensity d 68 ppm doublet of triplets 2 of doublets d -61 ppm triplet of doublets 1 of narrow triplets d 68 ppm triplets of quartets 1 230 K two higher-frequency resonances broaden and lose detail 300 K coalesced to a single broad line the lowest-frequency peak remained unchanged

42

ex. 3

spectrum of Rh5(13CO)15under pressure of 13CO (5 bar)

13C{1H}

43

ex. 4

spectrum of the CO region of (h5-C5H5)2Rh2(13CO)3

13C{1H}

44

ex. 5

31P{1H}

NMR spectra of [Ru2Cl5(PEtPh2)4Ag(PEtPh2)]

45

ex. 6 trans-[IrCl(CO)(PMe3)2] + SF4

Cl
F P SF3 Ir P CO

d 68 (2F)

-61 (1F)

-383 ppm (1F)

46

ex. 7 variable-temperature 1H NMR spectra of [Ru3W(C5H5)(CO)11H3]

47

ex. 8 EXSY 2D 1H NMR of Pt complex

48

solid state NMR spectroscopy difficulties immobility of the nuclei in solids (i) dipolar coupling are not averaged to zero ==> very broad resonance (ii) chemical shift anisotropy in solids is not averaged out ==> line broadening (iii) relaxation time T1 is very long ==> good signal-to-noise ratio is difficult to get solution: (i) magic angle sample spinning (MASS, MAS) technique an angle q = 54.7o to the magnetic field, the effect of chemically anisotropy can be averaged out (ii) cross-polarization (CP) technique overcome the problem of long relaxation time

49

ex. 1 13C NMR spectra of 2Ca(CH3CO2)2H2O

ex. 2 119Sn chemical shift of Ph3SnOH in solution d 80 ppm ==> 4-coordinated, tetrahedral in solid phase d 298 ppm ==> 5-coordinated similar to Me3SnF

50

ex. 3

chemical shift of phospha-alkene complex

31P

in solution d 31 ppm, JPt-P = 498 Hz ==> p-bonded ligand

in solid phase d 247 ppm, JPt-P = 4720 Hz ==> s-bonded ligand

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