13C-NMR Spectroscopy

12C common isotope is NMR inactive, have spin zero

13C isotope is NMR active because has some spin

Signal is very weak due to

• Low natural abdunace (1.03 %) and Total no of Carbons are normally low as compared to protons

• Magnatogyric ratio of Carbon is low as compare to proton, precess at low frequency as compared to 1H.
 C Spectra are easier to analyze than 1H spectra because the signals are not split. Each type of
13

carbon atom appears as a single peak.

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• The lack of splitting in a 13
C spectrum is a consequence of the low natural
abundance of 13C.
• Recall that splitting occurs when two NMR active nuclei—like two protons—are
close to each other. Because of the low natural abundance of 13C nuclei (1.1%), the
chance of two 13C nuclei being bonded to each other is very small (0.01%), and so
no carbon-carbon splitting is observed.
• A 13C NMR signal can also be split by nearby protons. This 1H-13C splitting is usually
eliminated from the spectrum by using an instrumental technique that decouples the
proton-carbon interactions, so that every peak in a 13C NMR spectrum appears as a
singlet.
• The two features of a 13C NMR spectrum that provide the most structural information
are the number of signals observed and the chemical shifts of those signals.

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• The number of signals in a 13C spectrum gives the number of different types of
carbon atoms in a molecule.
• Because 13C NMR signals are not split, the number of signals equals the number
of lines in the 13C spectrum.
• In contrast to the 1H NMR situation, peak intensity is not proportional to the
number of absorbing carbons, so 13C NMR signals are not integrated.

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 Nuclear Magnetic Resonance Spectroscopy
13
C NMR—Position of Signals
• In contrast to the small range of chemical shifts in 1H NMR (1-10 ppm
usually), 13C NMR absorptions occur over a much broader range (0-220
ppm).
• The chemical shifts of carbon atoms in 13C NMR depend on the same
effects as the chemical shifts of protons in 1H NMR.

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* At low frequency the excess population is reduced, sensitivity is very less.

* Normally 13C nuclei require one fourth of frequency as compare to 1H.

* 13C require higher scans and Pulse fourier transform instrument is easy to switch the frequency

* Chemical shift values of carbons have range 0-220 ppm (large range is due to different types of carbons)

Saturated carbons appear in range 0-60 ppm

Unsatured and aromatic carbons appear in the range 70-160 ppm

Carbonyl carbons appear 170-220 ppm

Deshielding effects are more effective as compare to 1H-NMR chemical shifts

Types of 13C spectra

1H coupled spectrum

1H decoupled spectrum

a) 1H coupled 13C spectrum

1H attached directly to “C” can easily effect the spin, and splits the signals according to the (n+1) rule

(heteronuclear coupling),

Spectra are known as proton coupled 13C spectra

1H-Decoupled Spectrum
More simple as compre to coupled (1H) spectrum

Disadvantage (give only information about “C” (no information about the protons attached to it)

Protons are constantly irradiated until those attain the saturation (change the spin states constantly)

Second radio frequency generator is used called (decoupler)

Off-resonance decoupling

Advantage of decoupling is that all signals appear as singlet

Disadvantage is that no longer has information about no of protons directly attached.

Off resonance decoupling technique is used to obtain the multiple information's

In an off-resonance-decoupled 13C spectrum, the coupling between each carbon atom and each
hydrogen attached directly to it is observed.

The n + 1 Rule can be used to determine whether a given carbon atom has three, two, one, or no hydrogens
attached. However, when off-resonance de- coupling is used, the apparent magnitude of the coupling constants is
reduced, and overlap of the resulting multiplet is a less frequent problem.

The off-resonance-decoupled spectrum retains the couplings between the carbon atom and directly attached
protons (the one-bond couplings) but effectively removes the couplings between the carbon and more remote
protons.
In this technique, the frequency of a second radiofrequency transmitter (the decoupler) is set either up field
or downfield from the usual sweep width of a normal proton spectrum (i.e., off resonance).

In contrast, the frequency of the decoupler is set to coincide exactly with the range of proton
resonances in a true decoupling experiment.

Furthermore, in off-resonance decoupling, the power of the decoupling oscillator is held low to avoid
complete decoupling.
DEPT Spectrum
Off resonance is old fashioned technique

Distortionless enhancement polarization transfer technique (DEPT)

More compatible with FT-instrument

Requires lot of computer programming

Gives the same information but in more reliable way

In the DEPT technique, the sample is irradiated with a complex sequence of pulses in
both the I3c and 'H channels.

The result of these pulse sequences is that the 13c signals for the carbon atoms in the
molecule will exhibit different phases, depending on the number of hydrogen's attached
to each carbon.

Each type of carbon will behave slightly differently, depending on the duration of the
complex pulses. These differences can be detected, and spectra produced in each
experiment can be plotted.
One common method of presenting the results of a DEPT experiment is to plot
four different Sub spectra.

Each sub spectrum provides different information.

A sample DEPT plot for isopentyl acetate is shown below

 All carbons appear but phase is different

CH2

Signals due to protonated carbon has only single H

Signals due to protonated carbon

NOE, Nuclear Overhauser Enhancement
Increase in the intensity of “C” due to the presence of directly attached protons is called
“Nuclear Overhauser Enhancement effect”

Hetronuclear effect operates between dissimilar atoms

This can be either positive or negative

Enhansement is positive if the proton is directly attached to the “C”