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Nuclear Overhauser Effect (NOE) and

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413 views12 pages

Nuclear Overhauser Effect (NOE) and

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kannemma084
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Nuclear Overhauser Effect (NOE) and

its effects in NMR spectroscopy

Nuclear spin polarization could be enhanced


by the microwave irradiation of the
conduction electrons in certain metals
Albert Overhauser 1953
Nuclear Overhauser Effect (NOE)
• When we obtain a proton-decoupled 13C spectrum, the
intensities of many of the carbon resonances increase
significantly above those observed in a proton-coupled
experiment.
• Carbon atoms with hydrogen atoms directly attached
are enhanced the most, and the enhancement increases
(but not always linearly) as more hydrogens are
attached.
• This effect is known as the nuclear Overhauser effect,
and the degree of increase in the signal is called the
nuclear Overhauser enhancement (NOE)
• The NOE effect is heteronuclear in this case, operating between
two dissimilar atoms (carbon and hydrogen). Both atoms exhibit
spins and are NMR active.
• The nuclear Overhauser effect is general, showing up when one of
two different types of atoms is irradiated while the NMR spectrum
of the other type is determined.
• If the absorption intensities of the observed (i.e., non-irradiated)
atom change, enhancement has occurred.
• The effect can be either positive or negative, depending on which
atom types are involved.
• In the case of 13C interacting with 1H, the effect is positive;
irradiating the hydrogens increases the intensities of the carbon
signals.
• The maximum enhancement that can be observed is given by the
relationship
• where irr is the magnetogyric ratio of the
nucleus being irradiated, and obs is that of the
nucleus being observed.
• Remember that NOEmax is the enhancement
of the signal, and it must be added to the
original signal strength:
• For a proton-decoupled 13C spectrum, we
would calculate,
• In dimethylformamide, for instance, the two methyl groups
are nonequivalent, showing two peaks at 31.1 and 36.2 ppm,
because free rotation is restricted about the C-N bond due to
resonance interaction between the lone pair on nitrogen and
the π bond of the carbonyl group.

Irradiation of the aldehyde hydrogen leads to a larger NOE for the carbon of the syn
methyl group (36.2 ppm) than for that of the anti methyl group (31.1 ppm), allowing the
peaks to be assigned. The syn methyl group is closer to the aldehyde hydrogen.
Reasons for Enhancement
• Signal enhancement due to NOE is an example of cross-
polarization, in which a polarization of the spin states in on type of
nucleus causes a polarization of the spin states in another nucleus.
• In the current example (proton-decoupled 13C spectra), when the
hydrogens in the molecule are irradiated, they become saturated
and attain a distribution of spins very different from their
equilibrium (Boltzmann) state.
• There are more spins than normal in the excited state. Due to the
interaction of spin dipoles, the spins of the carbon nuclei “sense” the
spin imbalance of the hydrogen nuclei and begin to adjust
themselves to a new equilibrium state that has more spins in the
lower state. This increase of population in the lower spin state of
carbon increases the intensity of the NMR signal.
HOW MUCH INCREASE?

• In a proton-decoupled 13C spectrum, the total


NOE for a given carbon increases as the
number of nearby hydrogens increases. Thus,
we usually find that the intensities of the
signals in a 13C spectrum
• (assuming a single carbon of each type)
assume the order CH3 > CH2 > CH >> C
Figure 6.11 is a proton-decoupled 13C spectrum of cyclohexanol. This
compound has a plane of symmetry passing through its hydroxyl group, and it
shows only four carbon resonances. Carbons a and c are doubled due to
symmetry and give rise to larger peaks than carbons b and d. Carbon d,
bearing the hydroxyl group, is deshielded by oxygen and has its peak at 70.0
ppm. Notice that this peak has lower intensity because the carbon d peak
receives the least amount of NOE; there is only one hydrogen attached to the
hydroxyl carbon, whereas each of the other carbons has two hydrogens.
TYPE OF DATA AQUISION IN DECOUPLING EXPERIMENT
AND NOE EXPERIMENT
In a decoupling experiment (HOMODEC) the B1 irradiation
must be on during acquisition of the FID (but not necessarily
otherwise), and in an NOE experiment the decoupler is on
during a delay period, but may be turned off during the
acquisition of the FID.
• Carbon attached to a double bond is deshielded due to its sp2 hybridization and some
diamagnetic anisotropy. This effect can be seen in the 13C NMR spectrum of cyclohexene (Fig.
6.12). Cyclohexene has a plane of symmetry that runs perpendicular to the double bond. As a
result, we observe only three absorption peaks. There are two of each type of carbon. Each of
the double-bond carbons c has only one hydrogen, whereas each of the remaining carbons
has two. As a result of a reduced NOE, the double-bond carbons have a lower-intensity peak
in the spectrum
• For example, notice in Figure 6.10 that the peak at 29 ppm (b) is much
larger than the others. This peak is generated by three carbons. The
quaternary carbon at 30 ppm (c) is very weak. Since no hydrogens are
attached to this carbon, there is very little NOE enhancement. Without
attached hydrogen atoms, relaxation times are also longer than for other
carbon atoms. Quaternary carbons, those with no hydrogens attached,
frequently appear as weak peaks in proton-decoupled 13C NMR spectra

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