Nuclear Magnetic Resonance

(NMR) Spectroscopy
Physical Principles:
• Some (but not all) nuclei, such as
1H, 13C, 19F, 31P and 15N have

nuclear spin.
• Nucleus spins about its axis
either clockwise or
counterclockwise
• Since the nucleus is charged, a
magnetic moment result from
nucleus spinning
 Cont. Physical Principles:
• Hence, nucleus is a tiny magnet with 2 possible
orientations (in the presence of an external
magnetic field).

• Upon application under external magnetic field, the ΔE=hν

random movement is directed either;

• It may either aligned with external magnetic field

α-state β-state
(low energy level= α-state) or against it (high energy
level= β-state)

• Each spin-active nucleus has a number of spins

defined by its overall spin, SAM (I= Spin Angular
Momentum).
 The rules for determining the net spin of a nucleus

• If no. of neutrons & no. of protons are both even, → NO spin (I= 0). e.g. 12C6.

• If no. of neutrons & no. of protons are both odd, then the nucleus has an
integer spin (I= 1, 2, 3, ….). e.g. deuterium 2H1.

• If no. of neutrons + no. of protons is odd, then the nucleus has a half-integer
spin (I= 1/2, 3/2, 5/2, ….). e.g. 13C6 and proton 1H.

• Only nuclei with I > 0 have magnetis properties.

• Practically nuclei with half-integral spin nuclei are detected using NMR as
they are simpler to detect.

• A nucleus of spin I will have 2I + 1 possible orientations.

Example: a nucleus with spin 1/2 will have 2 possible orientations.

These orientations represent the energy levels.
 Spin Quantum Numbers of Some Common Nuclei
The most abundant isotopes of C and O do not have spin.

Element 1H 2H 12C 13C 14N 16O 17O 19F

Nuclear Spin
Quantum No 1/2 1 0 1/2 1 0 5/2 1/2
(I)
No. of Spin 2 3 0 2 3 0 6 2
States
CLASSICAL INSTRUMENTATION

absorption
hn
signal
NMR Instrument
NMR Spectrum
When we look for a proton signal in 1H-NMR
spectrum, we can verify the following:

1. Chemical shift value (in ppm)

2. Splitting pattern (multiplicity, M): singlet,
doublet, triplet, quartet, .... and intensities
of signal lines.
3. Magnitude of coupling (J value in Hz).
4. Integration (signal intensity)
I- Chemical shifts (exact signal position in a NMR
spectrum) are measured relative to a reference of
a substance placed into the sample such as
tetramethylsilane (TMS) which is assigned zero
chemical shift.
 Tetramethylsilane

Solvent peak
 Protons in a Molecule
Depending on their chemical environment, protons in a
molecule are shielded by different amounts.
­ This is because a given nucleus is surrounded by
electrons which are also magnetic and, in the
presence of ext. magnetic field, these electrons
generate local magnetic field that opposes the main
NMR magnetic field.
The chemical shift is affected by 4 phenomena:
1- Electronegativity of neighboring groups or atoms
2- Hybridization
3- Hydrogen bonding
4- Magnetic anisotropy
1-Electronegativity of neighboring groups or atoms

Elements with high electronegativity such as F atom

withdraw the electrons that shield the protons by
inductive effect.
Deshielding of: F>Cl>Br>I

Compound δ (ppm)
(CH3)4Si =0
CH3I = 2.16
CH3Br = 2.65
CH3C1 = 3.10
CH3O = 3.50
CH3F = 4.24
Example on electronegativity: Chloroethane
 2- Hybridization

Redistribution of the energy of orbitals of individual

atoms to give orbitals of equivalent energy which
happens when two atomic orbitals combine to form a
hybrid orbital in a molecule.

sp2 hybridization results in a large downfield shift

sp2 orbitals hold electrons closer to the nucleus than the sp3 orbitals
do which means less shielding
And hence;
Shielding of hybridized orbitals

sp3 > sp2 > sp

sp Hybridization
sp hybridization is observed when one s and one p
orbital in the same main shell of an atom mix to form
two new equivalent orbitals. The new orbitals formed
are called sp hybridized orbitals. It forms linear
molecules with an angle of 180°

Ex; All compounds of a carbon-containing triple bond, like C2H2

sp2 Hybridization
sp2 hybridization is observed when one s and two p
orbitals of the same shell of an atom mix to form 3
equivalent orbitals. The new orbitals formed are
called sp2 hybrid orbitals

All the compounds of carbon, containing a carbon-carbon

double bond, Ethylene (C2H4)
sp3 Hybridization
hen one ‘s’ orbital and 3 ‘p’ orbitals belonging to the
same shell of an atom mix together to form four new
equivalent orbitals, the type of hybridization is called
a tetrahedral hybridization or sp3
Example: Hybridization in phosphorus pentachloride (PCl5)
 3-Hydrogen Bonding
• Inter-molecular or intra-molecular
hydrogen bonding leads to OH

deshielding of protons (down field O OH

shift of δ values).

• A clear example is the proton of the O O

H
5-OH group in flavonoid compounds
which is usually down field shifted
than that of the other OH groups in
other positions.
Examples on Intramolecular Hydrogen Bonding

ChemNMR 1H Estimation

5-OH
9.48
OH
6.72

6.92
O OH 9.48
7.11

7.15 6.93
6.33
H 4.8

3`& 4`-OH O O?
H
11.85

12 10 8 6 4 2 0
PPM

11.85 H
CHO O
10.36 6.96
H
7.56

O
7.72 7.20
OH

12 10 8 6 4 2 0
PPM
 4- Magnetic anisotropy
A secondary magnetic field produced by the π electrons of
for aromatic ring or double bonds.
Which make another (Third) magnetic field
[A] Protons of Benzene ring
protons inside the ring are highly shielded, against external mag. field
2.5 ppm

protons outside the ring are highly deshielded, with external mag. field
Benzene ring structure: the aromatic protons resonate at δ (6.5-9 ppm)

A B0 B B0

Shielded; Opposes B0 Deshielded; With B0

[B] Carbonyl (deshielding, affect to downfield): the aldehyde proton
resonates at δ (9.5-10 ppm)
[C] Acetylene (planner structure): at δ (2-3 ppm)

B0

Shielded

In the same direction as B0

Example on anisotropy: Ethyl benzene
II- Spin-Spin Splitting:
q Chemically equivalent protons do not couple
(magnetically interact) with each other.

q They appear at the same δ value as a singlet, and their

number is known from the integration.
3 1

2
O
CH2 O C CH3
2 1
3

Benzyl Acetate
Cont. II- Spin-spin Splitting
A-Indirect (J ) spin–spin coupling
è It is measured with the coupling constant “J ”, and is measured in
hertz (Hz) and is independent of the observation frequency.
H H H
H
è It is a measure of the interaction between a pair of protons not
C C C
beyond three bonds
è Two-bond coupling is called Geminal and three-bond coupling is
called Vicinal

H H
Two bond: Geminal H H Three bond: Vicinal
C C C
Splitting pattern and (n+1) Rule:

o As for multiplicity (M) of a proton

(splitting pattern), The resonance for a
set of protons will be split into:
M = n+1
o where n= number of protons on the
adjacent atoms.
In this case the signal appears as a doublet, triplet,
quartet, quintet, hextet, heptet or multiplet according to
the number of protons on the adjacent carbon atoms.

The number of splitting = (the number of the adjacent protons + 1)

The multiplicity and relative intensities may be
easily obtained from Pascal's triangle in which n
is the number of equivalently coupled protons.

-Multiplicity is often more complex than the simple n+1

rule because of:
ØThe presence of different types of neighbors.
ØThey couple differently, and more complex rules is
required.
No.of adjacent protons Pascal's triangle

Relative intensity Multiplicity

 Coupling constant J
• The extent of splitting (the -CH-CH3
distance between the lines) is
called the coupling constant (J
Value) and is measured (Hz).
 Significance of the Coupling Constant:

èThe coupling constant (J) of the coupled

protons [Ha-C-C-Hb] MUST BE EQUAL, Jab= Jba.

èThe J value varies according to the relation of

the coupled protons, i.e vicinal, geminal, cis,
trans, axial-axial, axial-equatorial, ortho, meta or
para, etc.
It ranges from say about 2 to 17 Hz.

èWe can obtain information about

stereochemistry from the value of the coupling
constant.
 Some important J values

Vicinal
Geminal

6-membered ring
Double bond system
 Cont. Some important J values

• In aromatic systems: o

• J -ortho = 7-10 ≈ 8 Hz
• J - meta, = 2 - 3 ≈ 2 Hz m

• J -para, =0-1 Hz. p

J value in glycosides
• In glycosides
• the J value of the anomeric protons'doublet is indicative
to the type of linkage between the sugar moieties and
the aglycones:
– In case of the β-D-configuration J value = 7-8 Hz
– In case of the α-D-configuration J value = 1-4 Hz
 Exchangeable protons
q Protons such as OH, NH, SH and COOH are
exchangeable with deuterium and acquired in certain
deuterated solvents (with no exchangeable protons e.g
DMSO).
q If drops of a deuterated solvent with exchangeable
proton (e.g D2O and CD3OD) is added and shaken with
the sample solution and the spectrum is rerun, the
signals corresponding to these protons will disappear
q The advantage of eliminating any contribution from an
exchangeable proton(s) is to simplify spectral
interpretation.
Examples on exchangeable proton

compare the two 1H NMR spectra

two different deuterated solvents.
Direct (dipolar) spin–spin coupling

qIt is the enhancement produced in the signal of a proton when a

nearby proton is irradiated.
qIt is very important on the study of the geometrical structure.
qIt is due to the through-space interaction of close nuclei leading to
increase on intensity of the signal of one nucleus Ha if its neighbor Hb
is irradiated provided that there is no normal coupling between them
qInterpreted from Nuclear Overhauser Enhancement (NOE) spectrum

H OH

H O
HO
H O
H OH
Ha
OH Hb

b-D-Glucoside
7.0

6.5 H3C H-2 OH integration

6.0
H-3 H-1
5.5
3

2.0
5.0

1.5 H-2 2 H-3

4.5
1.0 1

4.0 0.5
0
1.20
0.0
3.5 3.60

3.0

2.5

2.0

1.5

H-1 H-2 H-3

1.0

0.5

0.0
5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0