NMR spectroscopy

Dr. Santosh Kumar

Department of Chemistry,
HBTU Kanpur
02-01-2023
1
 Protons on Heteroatoms (N, S, O etc.): Proton Exchange
Reactions
Protons on a heteroatom differ from protons on a carbon atom as they are:
(i) exchangeable.

(ii) subject to hydrogen bonding.

(iii) Rapid chemical exchange causes Spin-spin decoupling or spin decoupling.

This cause decoupling of proton.

Fig.1. PMR spectrum of ethanol (neat, Fig.2. PMR spectrum of ethanol (pure, neat) at 60 MHz
2
acidified) at 60 MHz
Spectrum of pure anhydrous ethanol (Fig. 2) exhibits
(i) a triplet for -CH3 protons (c).
(ii) a multiplet consisting of eight lines for -CH2- protons (b). The -CH2- protons are under the influence of
two kinds of protons (-CH3 and -OH). Thus, the multiplet for -CH2- protons consists of (n + 1) (n' + 1) = (3
+ 1) (1 + 1) = 8 lines.
(iii) a triplet for -OH proton (a). The -OH appears as a triplet because of its coupling with -CH2- protons.

 Chemical exchange is catalyzed by acidic or basic impurities and high temperature.

 Rapid exchange and fast exchange is decoupled of proton. (if there is no rapid exchange then proton is
coupled)

Fig.1. PMR spectrum of ethanol (neat, Fig.2. PMR spectrum of ethanol (pure, neat) at 60 MHz
3
acidified) at 60 MHz
 Simpliflcation of Complex NMR Spectra
In case of complex molecule many PMR signals overlap or become buried in each other.

TMS
This causes difficulty in interpretation of PMR spectrum and hence to overcome this difficulties, some
techniques are used.

1. Use of high magnetic field:

We have noted that the chemical shift in Hz is directly proportional to the applied magnetic field, whereas
the value of coupling constant in Hz remains constant in different applied magnetic fields.

CH2 CH3 TMS

60 MHz

This will spread out the signals to make easy interpretation of

4
200 MHz the signals.
2. Double Irradiation (Double Resonance or Spin-spin decoupling)

Fig.3. PMR spectrum of acidified ethanol

Fig. 4. PMR spectrum of acidified ethanol on
double irradiation of methylene protons

5
3. Deuterium Exchange and Deuterium Labelling on deuteration

The protons of -OH, -NH2, -SH etc. groups are exchangeable with
D2O. Thus, such groups

are identified by exchange with D2O which causes their

signal to disappear from the spectrum. This exchange
reaction is similar to proton exchange reactions and is
called deuterium exchange reaction.
6
Deuterium labelling also simplifies PMR spectra as illustrated by the example of ethyl
chloride.

This deuterium labelling is interpretation of PMR by the changing the multiplicity of a signal.

7
4. Use of Shift Reagents
Shift reagents were first introduced by Hinckley in I969.
Shift reagents provide a useful method for spreading out normally overlapped PMR
absorption patterns without increasing the strength of the applied magnetic field.
The shift reagents are usually enolic ß-dicarbonyl complexes of a rare earth (lanthanide)
metal and these complexes are mild Lewis acids. Following are the structures of more
commonly used shift reagents Eu(dpm)3 and Eu(fod)3:

8
Fig.5. PMR spectrum of 1-hexanol at 100 MHz: (a) in the absence
of the shift reagent and (b) after addition of the shift reagent
Eu(dpm)3.
9
 Nuclear Overhauser Effect (NOE)
Let us take the example of 3-methyl-2-butenoic acid. If the vinyl hydrogen (cH) is irradiated, then the intensity of the
signal due to the methyl group a, which is cis to cH, becomes greater than that due to the trans methyl group b. On
irradiation of the cis methyl group a, cH shows an increase of 17% in the intensity of its absorption, whereas the
irradiation of relatively distant trans methyl groups b does not affect the intensity of the cH absorption.

 NOE originate in relaxation process.

 NOE is observable only over very short distances, generally 2-4 Å .
 Very strong intense radiofrequency (This is use in double irradiation).
 Very weak radiofrequency (This is use in NOE).
 When a proton or group of proton is irradiated by a very weak radio frequency the intensity of the absorption of
proton in close proximity to the irradiated proton is increased (either in +ve or –ve direction), this is called as Nuclear
Overhauser Effect (NOE). The increased in the intensity may be up to (~50%). Magnitude of intensity increased the
spatial closeness of proton.
 NOE is a space phenomenon.
 Its origin in relaxation process.
 This has do not spin-spin coupling.
 This is very useful in the study of stereochemical studies i.e., geometry of the molecule. 10
 Applications of PMR Spectroscopy

PMR spectroscopy is an important tool in the hands of organic chemists for getting
structural information. lt is also useful in stereochemical studies. An organic molecule
consists of carbon-hydrogen skeleton, and thus NMR spectroscopy is especially useful in
the study of this structural feature of the molecule. The important applications of PMR
spectroscopy, besides obtaining routine structural information, are summarized as follows:
I. Identification of Structural Isomers
II. Detection of Aromaticity
III.Detection of Hydrogen Bonding
IV.Distinction Between cis-trans Isomers and Conformers
V. Detection of Partial Double Bond Character
VI.Quantitative Analysis

11
 Type of PMR Spectroscopy

Two Types:
(1)Continuous Wave (CW) NMR Spectroscopy and
(2)Fourier Transform (FT) NMR Spectroscopy

Advantages of PMR Spectroscopy

1.It required very short time

2.Very small amount of sample
3.Very good quality of NMR spectra
12
 13C NMR Spectroscopy
The possibility of carbon NMR appears surprising at a first glance because
(i) the most abundant isotope of carbon 12C (natural abundance 98.9%) has no net nuclear spin (spin
number I is zero). Hence, it does not exhibit NMR phenomenon.
(ii) the far less abundant carbon isotope 13C (natural abundance only 1.1%) has (like 1H) a nuclear spin of
1/2 and is detectable by NMR.

 NMR has been discovered in 1950.

 Direct observation of carbon skeletons and carbon-containing functional groups by CMR on practical
basis has been available only since the early 1970s.

Theory
13Cand 1H both have same spin number I=1/2.
Theory is same as that of PMR because spin number I=1/2 is same.

13
 Experimental Recording

The same deuterated solvents are used in CMR spectroscopy which are used
in PMR spectroscopy, e.g., CDCI3, CD3COCD3, C6D6, CD3SOCD3 etc.

13C Chemical shifts

13C chemical shifts range from 0 to about 250 δ (compared to δ 0-15 for PMR) with
respect to TMS which is used as the common reference compound.

14
 General ranges of 13C chemical shifts

 Chemical shift in CMR are affected by the same factors as the PMR.

• Electronegativity increases δ value is also increases.

15
16
In PMR J = 0-20 Hz
In CMR J = 0-320 Hz

 13C-13C splitting is not observed because natural abundance of

13C is 1.1%. Due to very low natural abundance of 13C, It is

almost impossible to have two 13C on adjacent position linked

together molecule therefore splitting of 13C-13C is almost
negligible.

17