Академический Документы
Профессиональный Документы
Культура Документы
Molecular Spectroscopy
Nuclear magnetic resonance (NMR) spectroscopy: A spectroscopic technique that gives us information about the number and types of atoms in a molecule, for example, about the number and types of hydrogen atoms using 1H-NMR spectroscopy. carbon atoms using 13C-NMR spectroscopy. phosphorus atoms using 31P-NMR spectroscopy.
12
13
14
15
16
19
31
32
1/2 2
1 3
0 1
1/2 2
1 3
1/2 2
0 1/2 1/2 1 2 2
0 1
Nuclear Spins in B0
Within a collection of 1H and 13C atoms, nuclear spins are completely random in orientation. When placed in a strong external magnetic field of strength B0, however, interaction between nuclear spins and the applied magnetic field is quantized. The result is that only certain orientations of nuclear magnetic moments are allowed.
Nuclear Spins in B0
for 1H and 13C, only two orientations are allowed.
Nuclear Spins in B0
In an applied field strength of 7.05T the difference in energy between nuclear spin states for 1H is approximately 0.120 J (0.0286 cal)/mol, which corresponds to a frequency of 300 MHz (300,000,000 Hz). 13C is approximately 0.030 J (0.00715 cal)/mol, which corresponds to a frequency of 75MHz (75,000,000 Hz).
Nuclear Spin in B0
The energy difference between allowed spin states increases linearly with applied field strength. Values shown here are for 1H nuclei.
360 Hz 6 300 x 10 Hz
1.2 = 6 10
= 1.2 ppm
For a 1H-NMR spectrum, signals are reported by their shift from the 12 H signal in TMS. For a 13C-NMR spectrum, signals are reported by their shift from the 4 C signal in TMS. Chemical shift (): The shift in ppm of an NMR signal from the signal of TMS.
NMR Spectrometer
Schematic diagram of a nuclear magnetic resonance spectrometer.
NMR Spectrometer
Essentials of an NMR spectrometer are a powerful magnet, a radio-frequency generator, and a radio-frequency detector. The sample is dissolved in a solvent, most commonly CDCl3 or D2O, and placed in a sample tube which is then suspended in the magnetic field and set spinning. Using a Fourier transform NMR (FT-NMR) spectrometer, a spectrum can be recorded in about 2 seconds.
NMR Spectrum
1H-NMR spectrum of methyl acetate.
High frequency: The shift of an NMR signal to the left on the chart paper. Low frequency: The shift of an NMR signal to the right on the chart paper.
Equivalent Hydrogens
Equivalent hydrogens: Hydrogens that have the same chemical environment. A molecule with 1 set of equivalent hydrogens gives 1 NMR signal.
O CH3 CCH3 Propanone (Aceton e) H3 C ClCH 2 CH2 Cl H3 C 1,2-Dichloroethane Cyclope ntane C C CH3 CH3
2,3-Dime thyl2-bute ne
Equivalent Hydrogens
A molecule with 2 or more sets of equivalent hydrogens gives a different NMR signal for each set.
Cl CH3 CHCl 1,1-D ich loroeth ane (2 signals ) O Cyclop entan on e (2 s ign als) Cl C C H H (Z)-1-Ch loroprop ene (3 signals) Cyclohexen e (3 signals) CH3
Signal Areas
Relative areas of signals are proportional to the number of H giving rise to each signal, Modern NMR spectrometers electronically integrate and record the relative area of each signal.
Chemical Type of Hydrogen Shift () ( CH3 ) 4 Si 0 (by defin ition) RCH3 0.8-1.0 RCH2 R 1.2-1.4 R3 CH 1.4-1.7 R2 C= CRCH R2 1.6-2.6 RC CH 2.0-3.0 A rCH3 2.2-2.5 A rCH2 R 2.3-2.8 ROH 0.5-6.0 RCH2 OH 3.4-4.0 RCH2 OR 3.3-4.0 R2 NH 0.5-5.0 O RCCH 3 2.1-2.3 O RCCH 2 R 2.2-2.6
Type of Hydrogen O RCOCH3 O RCOCH2 R RCH 2 I RCH 2 Br RCH 2 Cl RCH 2 F A rOH R2 C= CH 2 R2 C= CHR A rH O RCH O RCOH
Chemical Shift () 3.7-3.9 4.1-4.7 3.1-3.3 3.4-3.6 3.6-3.8 4.4-4.5 4.5-4.7 4.6-5.0 5.0-5.7 6.5-8.5 9.5-10.1 10-13
Chemical Shift
Chemical shift depends on the (1) electronegativity of nearby atoms, (2) hybridization of adjacent atoms, and (3) diamagnetic effects from adjacent pi bonds. Electronegativity Electron eg- Chemical
CH3 -X CH3 F CH3 OH CH3 Cl CH3 Br CH3 I (CH3 ) 4 C (CH3 ) 4 Si ativity of X 4.0 3.5 3.1 2.8 2.5 2.1 1.8 Shift () 4.26 3.47 3.05 2.68 2.16 0.86 0.00
Chemical Shift
Hybridization of adjacent atoms.
Type of Hydrogen (R = alkyl) RCH3 , R2 CH2 , R3 CH R2 C=C(R)CHR2 RC CH R2 C=CHR, R2 C=CH2 RCHO N ame of Hydrogen Alk yl Allylic Acetylen ic Vin ylic Ald ehydic Chemical Sh ift () 0.8 - 1.7 1.6 - 2.6 2.0 - 3.0 4.6 - 5.7 9.5-10.1
Chemical Shift
Diamagnetic effects of pi bonds A carbon-carbon triple bond shields an acetylenic hydrogen and shifts its signal to lower frequency (to the right) to a smaller value. A carbon-carbon double bond deshields vinylic hydrogens and shifts their signal to higher frequency (to the left) to a larger value.
Type of H RCH3 RC CH R2 C=CH2 Chemical N ame Shift () Alk yl 0.8- 1.0 Acetylenic 2.0 - 3.0 Vin ylic 4.6 - 5.7
Chemical Shift
Magnetic induction in the p bonds of a carboncarbon triple bond shields an acetylenic hydrogen and shifts its signal lower frequency.
Chemical Shift
Magnetic induction in the p bond of a carboncarbon double bond deshields vinylic hydrogens and shifts their signal higher frequency.
Chemical Shift
The magnetic field induced by circulation of p electrons in an aromatic ring deshields the hydrogens on the ring and shifts their signal to higher frequency.
Signal Splitting (n + 1)
1H-NMR spectrum of 1,1-dichloroethane.
For this hydrogen, n = 3; CH3 - CH- Cl its signal is split into (3 + 1) = 4 peaks; a quartet Cl
Signal Splitting (n + 1)
Problem: Predict the number of 1H-NMR signals and the splitting pattern of each.
O (a) CH3 CCH2 CH 3 O (b) CH3 CH2 CCH2 CH3 O (c) CH3 CCH( CH3 ) 2
Coupling Constants
Coupling constant (J): The distance between peaks in a split signal, expressed in hertz. The value is a quantitative measure of the magnetic interaction of nuclei with coupled spins.
Ha Hb C C Ha Ha Hb Hb 8-14 Hz Ha C C Hb 11-18 Hz 5-10 Hz C C Hb C C Hb 0-5 Hz Hb 8-11 Hz 0-5 Hz Ha 0-5 Hz Ha H Hb a
6-8 Hz Ha
Signal Splitting
Pascals triangle.
As illustrated by the highlighted entries, each entry is the sum of the values immediately above it to the left and the right.
Coupling Constants
An important factor in vicinal coupling is the angle a between the C-H sigma bonds and whether or not it is fixed. Coupling is a maximum when a is 0 and 180; it is a minimum when a is 90.
Dichloromethane (achiral)
Homotopic atoms or groups have identical chemical shifts under all conditions.
Chlorofluoromethane (achiral)
Enantiotopic atoms or groups have identical chemical shifts in achiral environments. They have different chemical shifts in chiral environments.
H H 2-Butanol (chiral)
H D Chiral
3-Methyl-2-butanol
13C-NMR
Spectroscopy
Each nonequivalent 13C gives a different signal A 13C signal is split by the 1H bonded to it according to the (n + 1) rule. Coupling constants of 100-250 Hz are common, which means that there is often significant overlap between signals, and splitting patterns can be very difficult to determine. The most common mode of operation of a 13C-NMR spectrometer is a proton-decoupled mode.
13C-NMR
Spectroscopy
On the time scale of a 13C-NMR spectrum, each proton is in an average or effectively constant nuclear spin state, with the result that 1H-13C spin-spin interactions are not observed; they are decoupled.
13C-NMR
Spectroscopy