1. 13.14 13 C NMR Spectroscopy

2. 1 H and 13 C 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 1 H; it is standard practice for 13 C NMR

3. 1 H and 13 C NMR compared: 13 C 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 13 C nucleus is only about 1% as intense as that for 1 H 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 13 C (most are 12 C)

4. 1 H and 13 C NMR compared: 13 C signals are spread over a much wider range than 1 H signals making it easier to identify and count individual nuclei Figure 13.23 (a) shows the 1 H NMR spectrum of 1-chloropentane; Figure 13.23 (b) shows the 13 C spectrum. It is much easier to identify the compound as 1-chloropentane by its 13 C spectrum than by its 1 H spectrum.

5. 01.02.03.04.05.06.07.08.09.010.0 Chemical shift ( , ppm) ClCH 2 Figure 13.23(a) (page 572) CH3CH3CH3CH3 ClCH 2 CH 2 CH 2 CH 2 CH 3 1H1H1H1H

6. Chemical shift ( , ppm) Figure 13.23(b) (page 572) ClCH 2 CH 2 CH 2 CH 2 CH 3 020406080100120140160180200 13 C CDCl 3 a separate, distinct peak appears for each of the 5 carbons

7. 13.15 13 C Chemical Shifts are measured in ppm (  ) from the carbons of TMS

8. 13 C Chemical shifts are most affected by: electronegativity of groups attached to carbonelectronegativity of groups attached to carbon hybridization state of carbonhybridization state of carbon

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

10. Types of Carbons (CH 3 ) 3 CH CH4CH4CH4CH4 CH3CH3CH3CH3CH3CH3CH3CH3 CH 3 CH 2 CH 3 (CH 3 ) 4 C primarysecondary tertiary quaternary Classification Chemical shift,  1H1H1H1H 13 C 0.2 0.9 1.3 1.7-28 16 25 28 Replacing H by C (more electronegative) deshields C to which it is attached.

11. Electronegativity effects on CH 3 CH3FCH3FCH3FCH3F CH4CH4CH4CH4 CH 3 NH 2 CH 3 OH Chemical shift,  1H1H1H1H0.2 2.5 3.4 4.3 13 C -2 27 50 75

12. Electronegativity effects and chain length Chemical shift,  Cl CH 2 CH 3 4533292214 Deshielding effect of Cl decreases as number of bonds between Cl and C increases.

13. 13 C Chemical shifts are most affected by: electronegativity of groups attached to carbonelectronegativity of groups attached to carbon hybridization state of carbonhybridization state of carbon

14. Hybridization effects sp 3 hybridized carbon is more shielded than sp 2 114 138 36 36126-142 sp hybridized carbon is more shielded than sp 2, but less shielded than sp 3 CH 3 HCC CH 2 6884222013

15. Carbonyl carbons are especially deshielded O CH 2 C O CH 3 127-134 411461171

16. Table 13.3 (p 573) Type of carbon Chemical shift (  ), ppm Type of carbon Chemical shift (  ), ppm RCH3RCH3RCH3RCH30-35 CR2CR2CR2CR2 R2CR2CR2CR2C65-90 CRCRCRCR RCRCRCRC R2CH2R2CH2R2CH2R2CH215-40 R3CHR3CHR3CHR3CH25-50 R4CR4CR4CR4C30-40 100-150 110-175

17. Table 13.3 (p 573) Type of carbon Chemical shift (  ), ppm Type of carbon Chemical shift (  ), ppm RCH 2 Br 20-40 RCH 2 Cl 25-50 35-50 RCH 2 NH 2 50-65 RCH 2 OH RCH 2 OR 50-65 RCOR O160-185 RCRRCRRCRRCRO190-220 RCRCRCRCN 110-125

18. 13.16 13 C NMR and Peak Intensities Pulse-FT NMR distorts intensities of signals. Therefore, peak heights and areas can be deceptive.

19. CH 3 OH Figure 13.24 (page 576) Chemical shift ( , ppm) 020406080100120140160180200 7 carbons give 7 signals, but intensities are not equal

20. 13.17 13 C—H Coupling

21. 13 C— 13 C splitting is not seen because the probability of two 13 C nuclei being in the same molecule is very small. 13 C— 1 H splitting is not seen because spectrum is measured under conditions that suppress this splitting (broadband decoupling). Peaks in a 13 C NMR spectrum are typically singlets

22. 13.18 Using DEPT to Count the Hydrogens Attached to 13 C Distortionless Enhancement of Polarization Transfer

23. 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 13 C NMR spectrum involves

24. 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 13 C NMR spectrum involves

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

26. Chemical shift ( , ppm) 020406080100120140160180200 Figure 13.26 (a) (page 578) OC C CH CHCH CH 2 CH 3 CCH 2 CH 2 CH 2 CH 3 O

27. Chemical shift ( , ppm) 020406080100120140160180200 Figure 13.23 (b) (page 578) CH CHCH CH 2 CH 3 CCH 2 CH 2 CH 2 CH 3 O CH and CH 3 unaffected C and C=O nulled CH 2 inverted

28. 13.19 2D NMR: COSY AND HETCOR

29. 1D NMR = 1 frequency axis 2D NMR = 2 frequency axes COSY = Correlated Spectroscopy 1 H- 1 H COSY provides connectivity information by allowing one to identify spin-coupled protons. x,y-coordinates of cross peaks are spin-coupled protons 2D NMR Terminology

30. 1 H- 1 H COSY CH 3 CCH 2 CH 2 CH 2 CH 3 O 1H1H 1H1H

31. 1 H and 13 C spectra plotted separately on two frequency axes Coordinates of cross peak connect signal of carbon to protons that are bonded to it. HETCOR

32. 1 H- 13 C HETCOR CH 3 CCH 2 CH 2 CH 2 CH 3 O 13 C 1H1H