Nuclear Magnetic Resonance

Spectroscopy
Nuclear magnetic resonance (NMR) spectroscopy is
one of the most important methods of analysis to
reach the composition of compounds, as the analysis
provides information on the molecular structure of
organic compounds by examining the magnetic
properties of certain atoms within the molecule, and
the possibility of looking at hydrogen atoms (protons)
has become of particular importance.
Nuclear magnetic resonance spectrometry
measurements can be performed on nuclei
with an odd number of masses C13, N15,
F19, P31, H1, as well as for nuclei with even
mass and odd atomic numbers B10, N14,
H2 and there are some nuclei that do not
give signals NMR, although the previous
specifications apply to it. For example,
fluoride is the only halogen whose atoms
can be used in the work of the NMR .
• When using the nucleus of a hydrogen atom (proton) as a
model (1HNMR), the proton can be viewed as a positive unit
in a state of self-spin that generates a small magnetic field H
along the spin axis due to its rotation. If this nucleus is placed
in an external magnetic field B0, it will be directed (oriented) to
parallel spin α or opposite spin β to the direction of the
external field. Parallel spin is less energy than the opposite,
but the difference between the two directions is very small.

Parallel spin α and opposite spin to the direction of the

external magnetic field
When the external field is equal to zero, the two directions
of spinning are equal in energy and the difference increases
with the increase of the external magnetic field. When the
external field is equivalent to, BX, the difference in energy is
explained as follows
• Where μ is the magnetic moment of the nucleus in
the field and I equals 1/2, ΔE is the difference in
energy between the two directions of parallel spin
α or opposite β. The value of this difference in
energy (ΔE) in the NMR spectrum is given as a
frequency measured in units of MHz (106 Hz) in a
measurement from 20 to 900 MHz depending on
the strength of the magnetic field and the type of
nuclei under study.
• The difference in energy between the two
directions of spin at the strength of applied
magnetic field is relative to its magnetic moments.
For example, for the following nuclei, it would be:
1H μ = 2.7927, 19F μ = 2.6273, 31P μ = 1.1305
13C μ = 0.7022.
In general, nuclei composed of an odd number of protons (1H and
its isotopes, 14N 19F, and 31P) or an odd number of neutrons (13
C) show magnetic behavior. If both the proton and neutron counts
are even (12C or 16O) the nuclei are non-‐magnetic.
Where h = Planck's constant = 6.626069 10-34 J.s) External
magnetic field B0 = 2.35 T, Tesla is the unit of magnetic field
measurement, T .
• The proton converts from the parallel state to the opposite state it is
called resonance state. The energy absorption then its associated
emission are observed and recorded by a radio-frequency receiver
in the form of a peak in the HNMR spectrum, and the difference
between the two states of self-spinning is characteristic of the type
of nucleus and the strength of the applied magnetic field.
The following figure shows a diagram of the nuclear
magnetic resonance spectrometer (device)
The sample is placed between the magnetic poles and
irradiated with radio waves

Schematic diagram of a nuclear magnetic resonance spectrometer

• The mathematical equations show that the frequency occurs at
resonance has directly proportional with magnetic field to which the
nucleus is obeyed, when, the relationship between the magnetic
field and the frequency increased, the separation between the
resonance peaks in the spectrum increase.
• The NMR spectrum is a graph of the amount of energy absorbed (I
or strength) versus magnetic field strength...
• The magnetic field to which the nucleus is exposed is not only the
dominant field. When a molecule is placed in a magnetic field, the
electrons in each atom form, by induction, small magnetic fields in
the opposite direction of the dominant field. Thus, the nucleus is
subject to an actual field, which is the final outcome of the external
field. and the many small induced fields of neighboring atoms.
An HNMR spectrum is a plot of the intensity of a peak against its
chemical shift, measured in parts per million (ppm).
Structural Information from Features of a
1H NMR Spectrum

• Position of signals: indicates what types of hydrogen the

molecule contains.
• Number of signals: indicates the number of different
types of hydrogen in a molecule.
• Intensity of signals: indicates the relative amounts (how
many) of each kind of hydrogen in the molecule.
• Spin-spin splitting of signals: gives further information of
the neighboring environment for the various hydrogens
in the molecule.
• Protons come to resonance in different molecular
conditions and in different values of the applied magnetic
field because the induced field can either strengthen or
weaken the external field B0.
• Generally, almost of induced fields oppose the external
field, then we need a higher external magnetic field to
bring proton to the state of resonance (inversion) and in
this case it is said that the proton is shielded and we
notice its absorption at the high of the field in the
spectrum
• When the induced field parallels the external field, it is
added to it, so we need lower values to bring the proton
to the resonant state, as this proton is not shielded
(deshielded) and the absorption appears in a lower field.
• Shielded and Deshielded are relative terms. To get to
quantitative measurements, we need a reference.
Tetramethylsilane (TMS) (CH3)4Si was chosen as a
reference because its protons absorb far to the right in
the NMR spectrum, while most other protons absorb in
the lower range of TMS.
• The absorption of a proton is called the CHEMICAL SHIFT, which is
the location along the spectrum at which resonance occurs for a
nucleus in a specific molecular medium, always recorded in relation to
a standard resonance peak. In the case of proton NMR spectra for
organic compounds, only resonance peak of the methyl group in TMS
is taken as a reference. and gives a value of zero.
• It uses a scale for the value of the chemical shift that does not depend
on frequency known as delta δ and expresses the chemical shift on
the delta scale in parts per million (ppm)
• Induced Molecular Magnetic Fields:
• Fields induced by sigma (σ) electrons
• Each hydrogen atom in an organic compound is bonded to a carbon,
oxygen, or any other atom by a σ bond.When applying an external
magnetic field that causes σ electrons to rotate, this leads to formed
a small molecular magnetic field opposite to B0,
• If the induced field is opposite to the external one, this leads to the
shielding the proton associated with the σ bond, which requires the
proton to reach the resonance state to a higher magnetic field, so
the proton is absorbed in a higher field compared to a detached
proton.
• The intensity of the induced field depends on the proton density near
the hydrogen atom in the σ bond, the higher electronic density, gives
greater induced field leads shift of the observed absorption to the
higher field, or to a lower value of δ. i.e
• δ;>CH- > -CH2- > -CH3
• FACTORS INFLUENCING CHEMICAL SHIFT
• ELECTRONEGATIVITy-SHIELDlNG AND D ESHIELDING
The electron density of the C-H covalent bond is affected
by the electronegativity of the atoms, the attraction of
electrons by neighboring groups with electronegativity
has a deshielding effect and the chemical shift away to
lower field and the value of δ becomes higher.

Compound (CH3)4C (CH3)3N (CH3)2O CH3F

δ 0.9 2.1 3.2 4.1

Compound (CH3)4Si (CH3)3P (CH3)2S CH3Cl

δ 0.0 0.9 2.1 3.0

The value of δ increases with the increase in the
electronegativity of the neighboring groups as well as
with the increase in their number.

Cpd. / Sub. X=Cl X=Br X=I X=OR X=SR

CH3X 3.0 2.7 2.1 3.1 2.1

CH2X2 5.3 5.0 3.9 4.4 3.7

CHX3 7.3 6.8 4.9 5.0

• Fields induced by π electrons
• The unsaturation has a deshielding effect, thus the value of
δ increases, and the induced magnetic fields resulting from
the influence of an external field on the π electrons are
directional (asymmetrical) Ananisotropic which support the
external field, therefore we need a lower field for
resonance, i.e. a chemical shift to a higher value of δ
• In benzene,, the π electrons are delocalized and
distributed around the ring, when affected by a external
field, the fields induced resulting from rotate π electrons
strengthen the external field, therefore resonance needs a
less field than needs in the case of alkyl protons, so the
aryl protons are deshielded and absorbed at a lower
frequency (magnetic field) .
The influence of an external field B0 on the π electrons of
benzene, the fields induced to rotate the π electrons are in
the direction of the applied field, and there is a similar
situation in the case of vinyl hydrogen atoms or aldehyde
hydrogen atoms.
• effect of solvent used in the spectrophotometer
• For the purpose of taking the NMR spectrum, the materials
under test must be dissolved, and carbon tetrachloride was
used as a solvent because it does not contain hydrogen and
due to its toxicity and insolubility of polar compounds, it was
replaced by deuterium solvents, because deuterium (isotope
of hydrogen) has a different magnetic moment and spin and
is not visible in the spectrum nmr proton.
Chloroform-d (CDCl3) is considered one of the most important
deuteronic solvents used in NMR measurements due to its
solubility and non-reactivity. Other solvents are used such as
deuterium oxide (D2O), benzene-d6 (C6D6) , acetone. -d6
(CD3COCD3) and DMSO-d6 (CD3SOCD3), but these solvents
contain π electrons and can help hydrogen bonding.
The chemical shift of different protons can change according
to the solvent used. The following table shows some
examples with dilute solutions of deuteronic solvents at .300
MHz.
 Some Typical 1H Chemical Shifts (δ values) in Selected Solvents

Solvent
CDCl3 C6D6 CD3COCD3 CD3SOCD3 CD3C≡N D2O
Compound
(CH3)3C–O–CH3
C–CH3 1.19 1.07 1.13 1.11 1.14 1.21
O–CH3 3.22 3.04 3.13 3.03 3.13 3.22
(CH3)3C–O–H
C–CH3 1.26 1.05 1.18 1.11 1.16 ---
O–H 1.65 1.55 3.10 4.19 2.18 ---
C6H5CH3 2.36 2.11 2.33
CH3 7.15- 7.00- 2.32 2.30 7.15- ---
C6H5 7.20 7.10 7.10-7.20 7.10-7.15 7.30 ---
(CH3)2C=O 2.17 1.55 2.09 2.09 2.08 2.22

From the table, a slight change is observed in the values of δ by about ±0.1
ppm in most cases, but in the spectra taken using benzene-d6, a slight
increase in the field appears for most of the C-H signals, but in the spectrum
of acetone, a shift occurs by about two times, this may be due to the effect of
electron collision π-π of the carbonyl with the electrons of the benzene ring
and this leads to a shielding effect on the neighbored groups
• The other remarkable things is in the spectrum of tert-
butanol in the DMSO solvent, when the hydroxyl protons
shift by about 2.5 ppm to the lower range compared to
the compound using chloroform D as a solvent, this is
due to the strong hydrogen bonds that form between the
OH alcohol and the sulfide oxygen of DMSO, because
the hydrogen bonds act to Removing the shielding as
well as protecting the protons from the rapid substitution
reactions that prevent spin-spin splitting.
Spin-Spin Interactions
When protons are neighbored to each other, their spinning affects each
other
C - C-
Hb Ha
The spin of the proton generates a magnetic moment, so if the spin of
the proton Hb in the previous formula is paralleled, the magnetic
moment is added to the applied magnetic field
Thus, the proton Ha senses a slightly stronger magnetic field and
reaches the resonance state in a slightly lower magnetic field strength.
if the neighboring proton is in antiparallel state, then its magnetic
moment reduces the field around the first proton, therefore it needs a
slightly stronger magnetic field to bring the proton to the resonant
state.
Since half of the Ha protons are spinning parallel and the other half
are opposite (antiparallel), it can be said that there are two types of Ha
protons in the molecule and the result is the appearance of two Ha
peaks instead of an one peak in the HNMR spectrum, the same case
for Hb. This condition is called splitting..
• The number of peaks resulting from spin-spin spilittings of a proton
or a group of chemically equivalent protons can be predicted by
calculating the number of non-equivalent neighboring protons of the
proton under study from the following relationship n + 1 where n is
the number of non-equivalent protons.
• For example, in the case of the spectrum of benzene, a single,
individual (ONLY ONE) absorption appears, because all protons are
equivalent, and the same is the case for TMS compound.

• In the case of para-xylene, there are protons of two methyl groups,

they are all equivalent, and protons of the ring are also all
equivalent. Thus, two individual signals appear in the spectrum, one
for the methyl protons and the other for the protons of the benzene
ring.
• It is possible to clarify more than the spectrum of 1.1-
dichloroethane, where the spectrum shows the presence
of two types of signals, one of which is a doublet signal
due to the methyl protons that are not symmetrical (non-
equivalent) with the other proton attached to the
secondary carbon atom, and this proton shows a quartet
signal because it is not symmetrical with another three
proton
• In the case of the spectrum of the compound 1,2-
dichloroethane, the protons show a single signal due to
symmetry (chemically equivalent)
 1,2-dichloroethane 1,1-dichloroethane

The inteaction between the spins of neighbored

protons is called spin-spin coupling, this results in
the appearance of absorption signals with
multiple peaks.
.
Typical Coupling Constants
So far we have emphasised vicinal coupling of H atoms on adjacent sp3 C atoms. This coupling
constant is typically about 6-8 Hz. Coupling is controlled by geometry and the orbitals involved
between the coupling nuclei and therefore other types of systems have slightly different coupling
constants as shown below:

Typical J couplings

Notes:

H atoms on a CH2 of a alkene don't have to be equivalent (depending on what substituents are on
the other end of the alkene). As a result they can couple to each other. This is a 2 bond coupling.
Coupling between H atoms that are more than 3 bonds is also possible and is known as "long
range coupling".
In general, the more bonds involved between the H that are coupling, the smaller the J value.
Long range coupling is more common with rigid systems including the pi bond systems of alkenes
and substituted benzenes.
The presence of different couplings (i.e. different J values) tends to lead to "complex coupling"
(more on that later).
 There are a number of rules by which resonance
peaks are distinguished.
• Splitting occurs between neighbored protons
• splitting occurs only between nuclei with different chemical shifts,
means between magnetically non-equivalent atoms.
• The number of peaks N into which the proton signals are divided is
increased with 1 more than the number of neighbored covalent protons
n, N= n+1
• When N = 2, absorption appears with a doublet signal from one
neighboring proton, and the two peaks are equal in intensity (1:1).
• When N = 3, absorption appears in a triplet signal from two
neighboring protons with an intensity of (1:2:1).
• When N = 4, absorption appears in a quartet signal from three
neighbored protons with an intensity of (1:3:3:1).
• A singlet signal appears when there is no influence of neighboring
protons.
The Effect of Non-‐Equivalent Neighboring Hydrogens

When non-‐equivalent hydrogen atoms are not separated

by at least one carbon or oxygen atom, an additional
phenomenon called “spin-‐spin splitting” or “spin-‐ spin
coupling” occurs.
instead of single peaks (singlets), more complex paderns occur
called multiplets (doublets, triplets or quartets).
The number and kind of hydrogen atoms directly adjacent to the
absorbing nuclei can be deduced from the multiplicity of the
peak.
Spin-‐spin splitting is usually observed only between
hydrogen atoms bound to the same carbon (geminal
coupling) or to adjacent carbons (vicinal coupling).
Hydrogen nuclei separated by more than two carbon atoms
(1,3 coupling) is usually negligible.
Finally, equivalent nuclei do not exhibit mutual
spin-‐spin splitting. Ethane exhibits only a
single line at δ = 0.85 ppm.
Splitting is observed only between nuclei with
different chemical shifts.
 The distance between the peaks of a single multiple
absorption is always constant and is called the coupling
constant (J) and is given in Hz..

‫اجهزة الط‬
• NMR spectrometers contain a device to collect the number of
protons by calculating the area under the peaks in the spectrum in
an integrative way that gives relative values for the number of
protons in the molecule
• In the spectrum of chloroacetic acid, there is a number of H atoms
one of hydroxyl and two of methylene group in a ratio of 2:1. This
ratio can be found through the integration values given in the
spectrum, which is 12.5: 24.8, which gives almost the same ratio as
the previous one.
Note that this gives a ratio, and not the absolute
number, of absorbing protons
 Chemical exchange and hydrogen bonding
The NMR spectrum of methanol shows a double band for
methyl protons and a quartet band for the OH proton, and this
is expected, but this does not appear except at very low
temperatures (-40 0C).
At room temperature, the spectrum is contrary to the previous
one, as it shows a single absorption of the OH proton and
another single one for the methyl, and the reason is due to the
fact that the methanol molecule suffers a rapid reaction with
each other at room temperature, in the presence of a trace of
acid
Substituted for an OH proton in a process called chemical
exchange, this exchange is so rapid that neighboring protons
cannot distinguish the difference in spin, thus it is affected by a
rate of zero spin value (+1/2 -1/2)
Primary and secondary amines suffer of the same effect.
• The importance of the chemical exchange process lies in the fact
that the chemical shift of OH and NH protons depends on the
solvent and concentration due to the hydrogen bond.
• At higher concentrations, absorption appears in the higher δ region
due to hydrogen bonding. In solvents that are bonded by hydrogen
bonds, the absorption of the OH proton shifts to lower magnetic
fields.
 Proton Chemical Shift Ranges*

Low
Field
Region High
‫منطقة‬ Field
‫مجال‬ Region
‫منطقة‬
‫منخفض‬ ‫مجال‬
‫مرتفع‬

* For samples in CDCl3 solution. The δ scale is relative to TMS at δ = 0.

CARBON-13 NMR SPECTROSCOPY

In a 1.9 T field the precession frequency of 13C is 20 MHz,

that for IH being 80 MHz and 12C being nonmagnetic . In
principle, therefore, it is not difficult to observe 13C NMR.
The magnetic moment of 13C is about one-quarter that of
IB, so that signals are inherently weaker, but the
overwhelming problem is that the natural abundance of 13C
is only 1.1 per cent. The problem in simple molecules can be
overcome by synthesizing 13C-enriched samples, but this is
of little value in complex molecules.
C-13 nucleus behaves like a little magnet, it means that it can also be aligned with an
external magnetic field or opposed to it. Again, the alignment where it is opposed to
the field is less stable (at a higher energy). It is possible to make it flip from the more
stable alignment to the less stable one by supplying exactly the right amount of
energy.

The energy needed to make this flip depends on the strength of the external
magnetic field used, but is usually in the range of energies found in radio
waves - at frequencies
The NMR spectroscopy of 13C is very
useful for structural determination.

H-‐Decoupling
1
• 13C Spectra are easier to analyze than 1H spectra because the
signal splitting can be avoided.
• Each type of carbon atom appears as a single peak with 1H-
decoupling.
The numbers of non-equivalent carbons in the isomers of C7H14 are clearly
demonstrated by the numbers of 13C peaks in their NMR spectra
 Chemical Shifts in 13C NMR
• 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.

Common 13C-‐‐NMR chemical shift values

The most significant factors affecting the chemical
shifts are:
•Electronegativity of the groups attached to the C
•Hybridisation of C
A simple correlation table of 13C chemical shifts is
shown below.
MULTIPLICITY
Both 13C and IH have I = 1\2 so that we should expect to
see coupling in the spectrum between (a) 13C_13C and (b)
13C-'H. The probability of two 13C atoms being together in
the same molecule is so low that 13C_ 13C couplings are
not usually observed. Couplings from 13C - 'H interaction
,these couplings should be observed in the 13C spectra.
However, these couplings make the 13C spectra extremely
complex, and they have been eliminated by decoupling

To eliminate the complicating effects of the proton

couplings in the 13C spectra , we must decouple the 'H
nuclei by double irradiation at their resonant frequencies
(80 MHz at 1.9 T, etc .) .
In off-resonance decoupling the one bond C-H couplings are
retained so the signal for a particular C is given by the
number of attached H in accord with n+1 rule. So, for
example, a -CH3 shows as a quartet and a -CH2- as a triplet.
DEPT C-NMR Spectra

As stated previously, normal 13C spectra are broadband decoupled. With the
development of more modern spectroscopic methods it has become possible to use a
programed sequences of radio frequency pulses to determine other structural features.

One of these techniques is known as DEPT (distortionless enhancement of

polarisation transfer) which can be used to give similar information to an off-resonance
decoupled spectra i.e. the number of attached H.

In a DEPT experiment, a sequence of pulses with various delay times are used to
create the DEPT spectra where -CH3 and CH peaks appear as normal and -CH2-
peaks appear inverted. Quaternary C are not usually seen. This way the number of H
attached to C can usually be deduced. An example of a DEPT is shown below for 2-
butanol (notice how the peak for the -CH2- points down) with the corresponding
broadband decoupled spectra.
•2D-NMR Spectra
So far the NMR spectral methods we have discussed have been one dimensional
(since they have a single chemical shift x coordinate axis).

•With the development of more advanced spectroscopic methods as computational

power has increased, it has become possible to obtain two dimensional spectra
.
•In two dimensional experiments, both the x and the y axes have chemical shift
scales and the 2D spectra are plotted as a grid like a map.

•Information is obtained from the spectra by looking at the peaks in the grid and
matching them to the x and y axes.

• COSY - Correlation Spectroscopy

• both axes correspond to the proton nmr spectra.
• the COSY spectra indicates which H atoms are coupling with each other.
• An example of a COSY is provided below.
•HETCOR - Heteronuclear Correlation Spectroscopy
• proton nmr spectra on one axis and the 13C nmr spectra on the other.
• the HETCOR spectra matches the H to the appropriate C.
COSY spectra
•The information on the H that are coupling with each other is obtained by looking at the peaks
inside the grid. These peaks are usually shown in a contour type format, like height intervals on a
map.
An example shown below, the COSY of ethyl 2-butenoate
•First look at the peak marked A in the top left corner. This peak indicates a coupling interaction
between the H at 6.9 ppm and the H at 1.8 ppm. This corresponds to the coupling of the
CH3 group and the adjacent H on the alkene.
•Similarly, the peak marked B indicates a coupling interaction between the H at 4.15 ppm and the
H at 1.25 ppm. This corresponds to the coupling of the CH2 and the CH3 in the ethyl group.
Notice that there are a second set of equivalent peaks, also marked A and Bon the other side of
the diagonal.
HETCOR spectra
•The information on how the H and C are matched is obtained by looking at the peaks inside the
grid. Again, these peaks are usually shown in a contour type format, like height intervals on a
map.
•In order to see where this information comes from, let's consider an example shown below, the
HETCOR of ethyl 2-butenoate.
•First look at the peak marked A near the middle of the grid. This peak indicates that the H at 4.1
ppm is attached to the C at 60 ppm. This corresponds to the -OCH2- group.
•Similarly, the peak marked B towards the top right in the grid indicates that the H at 1.85 ppm is
attached to the C at17 ppm. Since the H is a singlet, we know that this corresponds to the CH3-
group attached to the carbonyl in the acid part of the ester and not the CH3- group attached to the
-CH2- in the alcohol part of the ester.
.

Notice that the carbonyl

group from the ester has
no "match" since it has
no H attached in this
example