13C

NMR Spectroscopy

1H

and 13C NMR compared:

both give us information about the number of chemically nonequivalent nuclei (nonequivalent hydrogens or nonequivalent carbons)
both give us information about the environment of the nuclei (hybridization state, attached atoms, etc.) it is convenient to use FT-NMR techniques for 1H; it is standard practice for 13C NMR

4.5 Chemical Shift Equivalence

CSE = Interchangeability by a symmetry operation or by rapid mechanism. Ex. The CH3 groups of t-Butyl alcohol are CSE due to rapid rotation

4.5 CSE continued

75.5 MHz C/C coincident

150.9 MHz C/C are resolved

1H

and 13C NMR compared:

13C

requires FT-NMR because the signal for a carbon atom is 10-4 times weaker than the signal for a hydrogen atom

a signal for a 13C nucleus is only about 1% as intense as that for 1H because of the magnetic properties of the nuclei, and at the "natural abundance" level only 1.1% of all the C atoms in a sample are 13C (most are 12C)

1H

and 13C NMR compared:

13C

signals are spread over a much wider range than 1H signals making it easier to identify and count individual nuclei

Figure 13.23 (a) shows the 1H NMR spectrum of 1-chloropentane; Figure 13.23 (b) shows the 13C spectrum. It is much easier to identify the compound as 1-chloropentane by its 13C spectrum than by its 1H spectrum.

4.2.2-Chemical Shift Scale and Range

For a given spectrometer, the resonance frequency for C13 is about that Of H1. Example on a 400 MHz instrument the carbon spectrum would be Obtained at 100 MHz. The chemical shift range for C13 is larger than for H1, thus overlap of signals Is less frequently encountered (it still happens though). To a first approximation, C13 chemical shifts parallel those of H1

Proton Spectrum

1H

ClCH2CH2CH2CH2CH3

ClCH2

CH3

10.0

9.0

8.0

7.0

6.0

5.0

4.0

3.0

2.0

1.0

Chemical shift (, ppm)

Carbon Spectrum

13C

ClCH2CH2CH2CH2CH3
a separate, distinct peak appears for each of the 5 carbons

CDCl3

200

180

160

140

120

100

80

60

40

20

Chemical shift (, ppm)

13C

Chemical Shifts

are measured in ppm ()

from the carbons of TMS

13C

Chemical shifts are most affected by:

electronegativity of groups attached to carbon hybridization state of carbon

Electronegativity Effects Electronegativity has an even greater effect on 13C chemical shifts than it does on 1H chemical shifts.

Types of Carbons Classification

Chemical shift,
1H 13C

CH4 CH3CH3 CH3CH2CH3 (CH3)3CH primary secondary tertiary quaternary

0.2 0.9

-2 8

1.3
1.7

16
25 28

(CH3)4C

Replacing H by C (more electronegative) deshields C to which it is attached.

Electronegativity effects on CH3

Chemical shift,
1H 13C

CH4 CH3NH2 CH3OH CH3F

0.2 2.5

-2 27

3.4
4.3

50
75

Electronegativity effects and chain length

Cl Chemical shift,

CH2 45

CH2 33

CH2 29

CH2 22

CH3 14

Deshielding effect of Cl decreases as number of bonds between Cl and C increases.

13C

Chemical shifts are most affected by:

electronegativity of groups attached to carbon hybridization state of carbon

Hybridization effects

sp3 hybridized carbon is more shielded than sp2

sp hybridized carbon is more shielded than sp2, but less shielded than sp3

114

36 138 36 126-142

68

84

CH2 22

CH2 20

CH3 13

Carbonyl carbons are especially deshielded

O CH2 127-134 C O CH2 CH3

41

171

61

14

Table 13.3 (p 573)

Type of carbon Chemical shift (), Type of carbon ppm Chemical shift (), ppm

RCH3 R2CH2 R3CH R4C

0-35 15-40 25-50

RC R2C

CR CR2

65-90

100-150

110-175
30-40

Table 13.3 (p 573)

Type of carbon Chemical shift (), Type of carbon ppm Chemical shift (), ppm

RCH2Br RCH2Cl RCH2NH2 RCH2OH RCH2OR

20-40 25-50 35-50 50-65 50-65

RC O

110-125

RCOR
O RCR

160-185

190-220

13C

NMR and Peak Intensities

Pulse-FT NMR distorts intensities of signals. Therefore, peak heights and areas can be deceptive.

T1 varies widely for different types of carbons. Generally, T1s Decrease as the number of attached protons increases. T1s are measured by the Inversion-Recovery Method. T1s cover a range of several seconds for CH3 grps to over a min. for quat. Cs. A delay between pulses (5 x T1) is required for quantitative C13 spectra.

4.2.3-T1 Relaxation

Attached Protons Affect T1 and Signal Intensity CH3 7 carbons give 7 signals, but intensities are not equal OH

200

180

160

140

120

100

80

60

40

20

Chemical shift (, ppm)

4.4 Quantitative C13 Analysis

Inverse-gated and Rd > T1

Inverse-gated decoupling With Rd < T1

Std. H1 decoupled Spectrum of DEP Rd < T1

13CH

Coupling

Peaks in a 13C NMR spectrum are typically singlets

13C13C

splitting is not seen because the probability of two 13C nuclei being in the same molecule is very small.
13C1H

splitting is not seen because spectrum is measured under conditions that suppress this splitting (broadband decoupling).

H1 Decoupling Techniques
J values for C-H are typically 110-300 Hz (C-C-H and C-C-C-H are 0-60Hz) Thus a CH3 group would appear as a quartet, CH2-triplet CH-doublet etc. The H1 nuclei are irradiated with a broadband Rf to remove coupling to Carbon.

4.3 Interpretation of a Simple C13 Spectrum: Diethyl Phthalate

decoupled

coupled

Expansions: Additional splitting Is due to J2 and J3 couplings

Using DEPT to Count the Hydrogens Attached to 13C

Distortionless Enhancement of Polarization Transfer

Measuring a 13C NMR spectrum involves 1. Equilibration of the nuclei between the lower and higher spin states under the influence of a magnetic field 2. Application of a radiofrequency pulse to give an excess of nuclei in the higher spin state 3. Acquisition of free-induction decay data during the time interval in which the equilibrium distribution of nuclear spins is restored 4. Mathematical manipulation (Fourier transform) of the data to plot a spectrum

Measuring a 13C NMR spectrum involves Steps 2 and 3 can be repeated hundreds of times to enhance the signal-noise ratio 2. Application of a radiofrequency pulse to give an excess of nuclei in the higher spin state 3. Acquisition of free-induction decay data during the time interval in which the equilibrium distribution of nuclear spins is restored

Measuring a 13C NMR spectrum involves In DEPT, a second transmitter irradiates 1H during the sequence, which affects the appearance of the 13C spectrum. some 13C signals stay the same some 13C signals disappear some 13C signals are inverted

Proton Decoupled Spectrum

O
CCH2CH2CH2CH3 CH CH CH2 CH2 CH2 C CH3

O
C

CH

200

180

160

140

120

100

80

60

40

20

Chemical shift (, ppm)

DEPT Spectrum
O
CCH2CH2CH2CH3 CH CH CH CH3

CH and CH3 unaffected C and C=O nulled CH2 inverted

200 180 160 140 120 100 80

CH2
60 40

CH2 CH2
20 0

Chemical shift (, ppm)

4.6 Distortionless Enhancement by Polarization Transfer (DEPT)

Pulse sequence developed to determine the number of protons Directly attached to a carbon.

DEPT 90 deg. CH only

DEPT 135 deg. CH &CH3 up, CH2 down Std H1 decoupled spectrum DEPT is a helpful to determine proton inventory, but it does not Record Hs on heteroatoms; must correlate with H1 spectrum.

13.19 2D NMR: COSY AND HETCOR

2D NMR Terminology 1D NMR = 1 frequency axis 2D NMR = 2 frequency axes COSY = Correlated Spectroscopy
1H-1H

COSY provides connectivity information by allowing one to identify spin-coupled protons. x,y-coordinates of cross peaks are spin-coupled protons

1H-1H

COSY

1H

CH3CCH2CH2CH2CH3
1H

HETCOR
1H

and 13C spectra plotted separately on two frequency axes Coordinates of cross peak connect signal of carbon to protons that are bonded to it.

1H-13C

HETCOR

13C

CH3CCH2CH2CH2CH3
1H