NMR spectroscopy: Shielding

Electrons surrounding the nucleus also produce magnetic field.

Badd = -B

Blocal = B + Badd = B(1-)

N Blocal / 2N B / 2
Resonant frequencies being dependent on strength of
external magnetic field, are inconvenient to remember.

How to get rid of field-dependence?

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Chemical Shift
Resonant frequency recorded for a reference compound (denoted
by 0).

Si(CH3)4 (Tetramethyl silane) is commonly used reference in NMR

spectra of organic compounds. (Highly shielded, single intense peak,
volatile)
Shift in the resonant frequencies of sample with respect to reference
is recorded.
Chemical shift: = {( )/} 106 ppm

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Chemical Shift: Ethanol

TMS

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Factors affecting Chemical

Shift
Reference (TMS) protons are highly shielded. Hence, larger chemical
shift indicates greater extent of deshielding lower shielding
constant.
Shielding constant: = local + neighbour+ solvent
local : due to the shielding from the electrons immediately
surrounding the nucleus.
neighbour : due to the shielding from the neighbouring
environment
solvent : the contribution from solvent molecules.
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Chemical Shift: Ethanol

Intensity of peak proportional to number of protons corresponding to
the peak: Integrate to calculate area under the peak 1:2:3
TMS

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Phenylacetone: PMR

O
CH2 C CH3

The number of signals = number of distinct sets of equivalent protons

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Benzene: PMR spectrum

Single peak: (all protons equivalent)
Chemical shift indicates high
deshielding
How will the specta of methane,
ethane, ethene, ethyne look like?
Position of the peak in the spectrum?

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Number of peaks, intensities

Number of peaks equals the number of distinct sets of
equivalent protons.

Equivalent protons: Two protons are equivalent if the

compounds resulting from replacement of either of them by
identical substituent will be chemically identical same
molecular formula, structural formula and geometry
Intensity of a peak directly proportional to the number of
equivalent protons responsible for the peak.

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Equivalent protons
Two protons are equivalent if the compounds resulting from
replacement of either of them by identical substituent will be
chemically identical same molecular formula, structural formula and
geometry.
Homotopic hydrogen atoms: If in making these replacements, we
get the same compound, the hydrogen being replaced are said to be
chemically equivalent or homotopic. Homotopic atoms (or groups)
are chemical shift equivalent.
In H2C=C(CH3)2 replacement of H with Cl gives
H2C=CCH2Cl(CH3) + ClHC=C(CH3)2
Six methyl hydrogens form one set; replacing any one of them with
chlorine, for example, leads to the same compound. Two vinyl
hydrogens form another set; replacing either of these leads to same
compound. So 2-metylpropene gives two 1H NMR signals
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Equivalent protons
Enantiotopic hydrogen atoms: If replacement of each of two
hydrogen atoms by the same group yields compounds that are
enantiomers, the two hydrogen atoms are said to be enantiotopic.
Enantiotopic hydrogen atoms have the same chemical shift and give
only one 1H NMR signal.
In CH3CH2Br, two hydrogen atoms of -CH2Br group are enatiotopic.
Diastereotopic hydrogen atoms: If replacement of each of two
hydrogen atoms by the same group gives compounds that are
diastereomers, the two hydrogen atoms are said to be diastereotopic.
Diastereotopic hydrogen atoms do not have the same chemical shift
and gives rise to different 1H NMR signals.
The two protons of =CH2 group of ClHC=CH2 are diastereotopic.
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Examples to solve:
How many peaks will be present in the PMR spectra of the
following molecules? What will be the ratio of intensities?

HCHO
CH3COCH3
CH3CHO
CH3COCH2CH3
CH3CH=CHCH3
(CH3)2CH-CH2CH3
CH3COOCH3
CH3CH2CHClCH3

1
1
2
3
2
4
2
4

3:1
3:2:3
3:1
6:1:2:3
1:1
3:2:1:3

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Factors affecting Chemical

Shift
Reference (TMS) protons are highly shielded. Hence, larger chemical
shift indicates greater extent of deshielding lower shielding
constant.
Shielding constant: = local + neighbour+ solvent

Deshielding due to electronegative elements

Anisotropic effect : Shielding/deshielding due to ring currents
Other effects: Hydrogen bonding, solvent effects, etc.
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Deshielding due to
electronegative elements

No. of electronegative atoms Distance from the electronegative atom

CHCl3 CH2Cl2 CH3Cl
7.27

5.30

3.05 ppm

-CH2Br
3.30

-CH2CH2Br
1.69

-CH2CH2CH2Br
1.25

ppm

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Anisotropic effect: ethene, ethyne

shielded

deshielded
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Solvent contribution (solvent)

A proton on the solute molecule is shielded because of the anisotropic

effect produced as a result of ring current of benzene as solvent

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Typical Chemical Shift ranges

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Fine structure (Spin-spin coupling)

Ethanol

Each magnetic nucleus contributes to the local magnetic field of

other nuclei.
Spin- spin coupling constant J (Hz) is independent of the applied
magnetic field.
Consider AX where A and X are spin nuclei.
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Fine structure (Spin-spin coupling)

Consider the protons A and X (or in general spin nuclei)

In absence of any interaction between A and X, the total energy of these

two protons in a magnetic field B (neglecting spin-spin coupling) is
E = - N(1-A)BmA - N(1-X)BmX
Where, A and X are the shielding constants of A and X.
If the nuclei A and X are close enough in the molecule (separated by one
to three bonds, for example), their magnetic moments will perturb each
other. The spin-spin interaction energy will be
Espin-spin = hJAXmAmX
Etotal = E + Espin-spin = - NB{(1-A)mA + (1-X)mX} + hJAXmAmX
Four energy levels are obtained.
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Fine structure (Spin-spin coupling)

In absence of spin
spin coupling

In presence of spin
spin coupling
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Fine structure (Spin-spin coupling)

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Fine structure (Spin-spin coupling)

AX2

1 :2: 1
The two X nuclei may
have the 22 = 4 spin
arrangements. The
middle two
arrangements are
responsible for the
coincident resonance of
A.

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Fine structure (Spin-spin coupling)

AX3

1 :3 : 3 : 1
There are 23 = 8
arrangements of the
spins of the three X
nuclei, and their
effects on the A
nucleus gives rise to
four groups of
resonances.
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Fine structure (Spin-spin coupling)

N equivalent spin-1/2 nuclei split the resonance of a nearby spin
or group of equivalent spins into N+1 lines with an intensity
distribution. The relative intensities are given as coefficients of
the binomial expansion (1+x)n

This is given as Pascals triangle

1
1 1
1
2
1
1
3
3
1
1
4
6
4
1
1
5
10
10
5
1
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