NMR

Nuclear Magnetic Resonance
(NMR) Spectroscopy
CH-521 Course on Interpretative Molecular Spectroscopy; Course Instructor: Krishna P. Kaliappan 1

Nuclear Spin States
 Nuclei having odd atomic number, odd mass or both have quantized
spin angular momentum and magnetic moment.
 Such nuclei have a quantized angular spin quantum number (I).
 Number of spin states for that nuclei is defined by (2I+1), with
integral differences ranging from –I to +I.
m
m = Magnetic Moment
 In absence of any external magnetic field, all nuclear spin states

should be of the same energy and hence equally populated.
 In the presence of a magnetic field, the nuclear charge and spin
generates its own magnetic moment.

Some Common Nuclei
 Most notably, two of the most abundant nuclei in organic compounds

have zero spin- 12C and 16O.

Nuclear Magnetic Moments
 Hydrogen nucleus has I = ½.
m
Direction of External
Magnetic Field (B0)
m
Spin Aligned Spin Opposed
s = +1/2 s = -1/2
 Thus, in a magnetic field, hydrogen nucleus splits into its two spin
states- either aligned or opposed to the external magnetic field.
N N
S N Spin Opposed System:

Spin Aligned System:
Unstable; tries to spin
Stable N S
into alignment
S S

Nuclear Spin State Splitting
 Magnetic nuclei split into their corresponding spin states upon
exposure to magnetic field.
-3/2
-1/2 -1/2
E E
+1/2 +1/2
+3/2
No Field Applied Field No Field Applied Field
1Hnucleus 35Cl
nucleus
I = 1/2, 2 states I = 3/2, 4 states
 Spin aligned states are always lower in energy than spin opposed
states.
Nuclear Spin State Energies
 Stronger the applied magnetic field, greater will be the energy
difference (ΔE) between the spin states after splitting.
ΔE = γB0 … 1
 γ is the ratio between the magnetic moment and angular momentum of

a given nucleus. This ratio is called the Gyromagnetic Ratio.
 Gyromagnetic ratio is constant for a given nucleus and hence the

extent of splitting also depends on γ.
 Angular momentum is quantized in the form of (h/2π) units, eqn 1

becomes:
ΔE = γ(h/2π)B0 = hν … 2
 Frequency of the absorbed energy can be expressed as:
ν = (γ/2π)B0 … 3

Nuclear Spin State Energies
ν = (γ/2π)B0
 If the correct value of γ is substituted, we find that for an applied

field of 1.41 Tesla, a 1H nucleus would absorb at a frequency of 60
MHz, which is in the radiofrequency (RF) zone of the electromagnetic
spectrum.
 This is called the resonating frequency of the 1H nucleus.
Resonating frequencies of a few common nuclei

Precessional Motion
 Since a proton is a spinning magnet, it moves in a characteristic
fashion under influence of external magnetic field.
 This motion is called precessional motion, which is comparable to
the motion of a spinning top.
Opposed
DE = hn
Aligned
B0
 Energy difference is directly proportional to the magnetic field

strength.

Mechanism of Resonance
 Under the effect of an applied magnetic field, nuclei start precessing
along its axis with an angular frequency ω (Larmor Frequency).
w = 60 MHz
n = 60 MHz
hn
s = -1/2
s = +1/2
hn = hw
B0
 The nuclei being charged, generates an oscillating electric field having
the same frequency ω.
 Now if radiowaves of the same frequency are supplied to this
precessing nucleus, the two electric fields can couple and the energy
can be absorbed by the nucleus. This process is called resonance.
 Resonance is accompanied by a change in spin of the nucleus.

Spin State Population Density
 According to the Boltzmann distribution, calculated ratio of electrons
in upper and lower spin states of a proton nucleus at 298 K for an
instrument operating at 60 MHz is:
 This excess population of 9 electrons is extremely important as it is

responsible for resonance.
 With increase in instrument frequency, the energy gap between the

two spin states also increases. This leads to a greater population
excess in the lower state.
 Thus at higher instrument frequencies, more nuclei can undergo spin
transition and hence a stronger signal is generated (more sensitive).
 At extremely high instrument frequencies, population in each level

reaches an equilibrium, which leads to saturation. This should be
prevented.
The NMR Spectrometer
 Earlier Continuous Wave (CW) instruments have now been replaced by
modern Pulsed Fourier Transform (FT) Spectrometers.
 In CW instruments, all different types of protons were excited
individually and their resonance peaks were recorded independent of
the others.
 In modern FT instruments, a short burst of energy called a pulse is
supplied, which excites all protons in the sample at the same time.

NMR Instrument Probe
 The sample probe is exposed to the
magnetic field inside the instrument.
 Modern NMR spectrometers all contain

superconducting magnets cooled down to
liquid helium temperatures.
 The liquid helium chamber in turn, is

surrounded by liquid nitrogen for
further cooling.
 Superconducting magnets of 400 MHz

and 500 MHz frequency are very
common nowadays.

The NMR Pulse
A Pulse Frequency content of the pulse
 A pulse excites all target nuclei in the molecule.

 As a direct consequence of Heisenberg’s Uncertainty Principle,
because the pulse is for a very short time, it contains a wide range
of frequencies.
 This frequency range is wide enough to excite all different types of
proton nuclei in the sample.
 When the pulse is discontinued, the excited nuclei begin to lose their
energy and return to their original spin state. This process is called
relaxation.
Spin Relaxation and FID
 During relaxation of the excited nuclei, they emit electromagnetic
radiation.
 Since a variety of different types of protons were excited, radiations

of a whole range of frequencies would be emitted. This is called Free
Induction Decay (FID).
 The FID signal decays exponentially with time as the nuclei relax.
 Hence the FID is a time-domain signal.
 However, the frequency of the FID is not the exact frequency of the
nucleus as it is an interference signal between the supplied
radiofrequency and the frequency emitted by the excited nucleus.
 For any one type of proton, wavelength of the FID may be calculated
as:

FID and Fourier Transform
 A complex molecule will have various types of protons and hence the
FID will be a superposition of various frequencies, each having a
different decay rate!
 A Fourier Transform is a mathematical function which separates each
of the components of the wave and converts them to a frequency
domain.
FID for acetone in time domain FID signal in frequency domain after FT

Signal and Noise
 Noise is random electronic signals that appear as fluctuations of the
baseline in the spectrum.
 Since noise is random, its intensity does not increase with multiple
iterations of the spectrum added together.
 Hence the Signal:Noise ratio can be vastly improved by increasing the

number of scans (n) for the sample:

Advantages of FT-NMR
 In CW instruments, radiofrequency is slowly increased to resonate
protons individually.
 In FT NMR instruments, a pulse is given to resonate all the protons
at a time.
 FT NMR instruments are much faster than conventional CW
instruments as it takes seconds to measure an FID.
 The whole process being computer generated takes very less time for
very complicated processes like Fourier Transform.
 Multiple iterations can be given on the sample in additive manner to

improve the signal:noise ratio significantly.
 This helps in increasing sensitivity towards less abundant nuclei,

weakly magnetic nuclei and very dilute samples.

Magnetic Shielding
 If all protons absorb same amount of energy in a given magnetic
field, much information won’t be gathered.
 Spinning electrons create an induced magnetic field that opposes

the external magnetic field.
 Nuclei are surrounded by electrons that create a shield over them

from external magnetic field, & effective magnetic field
experienced by the nuclei would be -
Beffective = Bexternal - Binduced
 Changes in distribution of electrons around nuclei affects (i) net

magnetic field experienced by the nuclei, (ii) the frequency at which
the nuclei resonates.
 When a nucleus is covered with electronic cloud around it, it is

called shielded. If it is more exposed to external magnetic field, it
is called deshielded.

Chemical Shift & its Measurement
 In 1951, Packward observed three different precessional
frequencies of protons in EtOH. Since the shift in frequency was
due the chemical environment, it was named as chemical shift.
 Chemical shifts are expressed by δ (Delta), which are defined as

proportional differences in parts per million (ppm) from an
appropriate reference standard.
Internal Standard:
 Measurement of precessional frequencies of a group of nuclei is not

difficult but not required.
 Generally the difference in frequencies are measured with respect

to some reference group of nuclei. These are called internal
standards.
 Most common internal standard for 1H and 13C is tetramethylsilane

(TMS).

 Exact magnetic field experienced by a nucleus (Chemical shift)
could be expressed mathematically as -
Where δX is the chemical shift (in ppm).

νX and νTMS are frequencies of signals of X & TMS (in Hz).
ν0 is frequency of operating instrument (in MHz).
 Signals having higher δ values (more deshielded) are called

downfield signals & lower δ values (more shielded) are called upfield
signals.
OMe
Downfield 1H Upfield 1H

Criteria of Choosing Internal Standard:
 Should have equivalent nuclei (eg. In TMS all 12 H’s are equivalent).
 Should be chemically inert.
 Should have low boiling point, so that samples could be recovered.
 Should be soluble in most organic solvents.

 Should give one sharp signal in spectrum.
 TMS is commonly used for 1H, 13C NMR experiments.
 CFCl3 is used for 19F NMR experiments.

 Concentrated H3PO4 is used for 31P NMR experiments.

Factors Influencing Chemical Shifts
 Different types of protons appear with different δ values in spectrum.
1H Correlation Chart
 What could be the factors controlling chemical shift values of

protons, residing in different chemical environment?

1. Electronegativity Effect:
 Electronegative element attached to a nucleus, increases its chemical
shift value.
 Electron withdrawing groups attached to a carbon, withdraws valence

electron density around the protons attached to that carbon.
Compound CH3F CH3OH CH3Cl CH3Br CH3I CH4 (CH3)4Si

Element (X) F O Cl Br I H Si
Electronegativity of X 4.0 3.5 3.1 2.8 2.5 2.1 1.8
Chemical Shift (δ) (ppm) 4.26 3.40 3.05 2.68 2.16 0.23 0
 Multiple substituents have stronger effect than single substituent.

CHCl3 CH2Cl2 CH3Cl -CH2Br -CH2-CH2Br -CH2-CH2CH2Br
7.27 5.3 3.05 3.3 1.69 1.25

2. Mesomeric Effect:
 Alkenes:
d 6.52 d 3.74
d 5.29
H H H H
H H
H O H O CH3
H H
H3 C
 Mono-substituted Rings:
CH3 NO2
NH2 OMe
H d 7.13 H H d 8.21
H H d 6.55 H H d 6.87 H
d- d- d+ d+
d- d- d- d-
H d 7.25 H H H d+ H d 7.55
H d- H d 7.08 H d-
H d 7.25 H
H H
d 7.70
d 6.70 d 6.93

2. Mesomeric Effect:
NH2
OMe
CH3
NO2

3. Hybridization Effect:
Order of electronegativity: sp > sp2 > sp3 (Consider % of s-character).
Protons connected to sp3 carbons:

 Protons attached to sp3 carbons generally come within 0-2 ppm range.
C H H H
C C H C C H C C H
C C H H
2 d 1 0
 Decreasing order is due to higher electronegativity of carbon than

proton.
 Protons on a sp3 carbon which is further attached to some hetero

atom, will have higher δ value than 2 ppm.

Protons connected to sp2/sp carbons:
 Normal vinylic protons resonate within 5.5-7.0 ppm.

 Aldehyde protons resonate within 9.0-10.0 ppm.
 sp2 carbons (33% s) are more electronegative than sp3 carbons

(25% s) !!
 But only electronegativity can’t explain the reason for having so
higher δ values than aliphatic protons.
 Another effect, called magnetic anisotropy need to be considered.

Magnetic Anisotropy:
 When placed under a magnetic field, benzene π electrons are induced
to circulate around the ring. This circulation is called ring current.
H H
H H
H H
B0
 The circulating electrons generate a magnetic field that creates a

diamagnetic shielding zone inside the ring and paramagnetic deshielding
zone in periphery of the ring.
Diamagnetic shielding
H H
H H
H H
Paramagnetic
deshielding
 The aldehyde proton directly falls under paramagnetic deshielding
zone due to anisotropy of C=O bond π electrons
Shielding Shielding
zone zone
Deshielding C C Deshielding C O Deshielding

zone zone H zone
Shielding Shielding
zone zone
 Annular protons reside in diamagnetic shielding zone, whereas

outer protons fall in paramagnetic deshielding zone.
H H
H H
H H H
Annular protons H H
resonate at d -1.8 ppm H H
H H H
H H
H H
Outer protons resonate at d 8.9 ppm
 Some other examples of magnetic anisotropy in different class of
compounds.
~ d -1.0 ppm ~ d -4.0 ppm
COOH (shielded) H2 Me (shielded)
~ d -0.5 ppm
H2 C (shielded)
H2 C C CH2
H
H H2 C CH2
Me ~ d 8.0 ppm
~ d 2.0 ppm H (deshielded)
~ d -1.4 ppm
(shielded) (deshielded)
d 0.85 d 3.75
d 0.83 d -0.17 d 1.27 d 3.53
CH3 HO H
H H H3 C H OH
CH3
d 0.79 d 0.70 d 1.23 d 0.72

H CH3 H3 C H H3 C CH3

 Although sp carbons are more electronegative than sp2 carbons,
alkynic protons resonate in much upfield (lower δ value) range than
olefinic protons.
Deshielding zone
Shielding zone
 In alkynes, the induced magnetic field generated due to circulating π

electrons, shields alkynic protons.
 So, the alkynic protons experience much less magnetic field strength
than olefinic protons, as a result they appear in spectrum with a low
δ value.

 Some representative examples to show the difference in chemical
shift values of olefinic and alkynic protons.

 Cyclopropane is very strained and has double bond character, which
generates a magnetic dipole like alkenes/arenes.
 However, in cyclopropane the protons fall in shielding region and
resonates at δ 0.8-0.2.
Shielding zone
H H H
Deshielding zone
H H
H
 Spiro cyclopropane ring also can exert the same effect.
O O
H H H H
d 7.42 d 6.91
 In this case induced magnetic field of cyclopropane ring shields
these protons.
 Like double bonds and triple bonds, single bonds also can exert
anisotropic effect.
 In cyclic systems such effect plays a role.

 Rapid ring flipping shows only one
peak at room temperature. But it
shows two distinct peaks at -70 oC.
 Due to magnetic anisotropy,
equatorial protons resonate in slight
deshielded zone.

4. Exchangeable Protons:
 Deuterium exchange is highly concentration and time dependent.
 Acids, phenols, alcohols and amines show deuterium exchange with
protons most readily.
RCOOH 10.5-12.0 ppm
ArOH 4.0-7.0 ppm
ROH 0.5-5.0 ppm
RNH2 0.5-5.0 ppm
RCONH2 5.0-8.0 ppm
CH=CH-OH > 15.0 ppm
 Acidic protons are highly deshielded because of electronegativity

and resonance.
O O
H H
R O R O
 When an acidic compound gets dissolved in D2O, acidic protons get

exchanged with deuterium and a new signal generates for HOD.

 In normal amines the rate of exchange is very high. This could be
hindered by making the solution acidic, so that amines get
protonated. + H
H2N R H3N R
pH < 1
 Rapid intermolecular proton exchange often leads to peak broadening.

 This phenomenon is time dependent. Peak coalescence is observed
when rate of exchange is comparable with NMR time scale.

5. Hydrogen Bonding:
 Protons that can exhibit H-bonding, exhibit variable absorption
over a wide range.
 H-bonding involves electron-cloud transfer from H-atom to nearest
electronegative atom. So, H-bonded H’s experience a deshielding
effect.
 The more H-bonding takes place, the more deshielded the proton
becomes.
 Extent of H-bonding is a function of concentration and
temperature. In concentrated solutions extent of H-bonding is
more.
H H H
O O O O
R H
R R R
Free molecule
(high dilution) Hydrogen bonded
(Concentrated solution)
 At high dilution hydroxyl protons resonate near 0.5-1.0 ppm. In

concentrated solutions they appear close to 4.0-5.0 ppm.
5. Hydrogen Bonding:
 Increased temperature reduces intermolecular hydrogen bonding.
So, resonance position for these protons are highly temperature-
dependent.
 Intramolecular H-bonding remains unchanged after dilution. So,
chemical shift values also do not change after dilution.
d 10-12 d 11-16
O H
H
O O
O
R1 R2
OR
Salicylates Enols
 Carboxylic acids are stable in their dimeric form, which even

persist in very dilute solution.
d 10-13
O H O
O H O
Carboxylic acid dimer

6. Effect of Solvents:
 In polar solvents, there will be much stronger dipolar interaction
between solute & solvent specially in polar compounds.
 Interaction between a polar solvent and a polar solute is more than
that of TMS, leading to a shift in δ value with respect to TMS.

6. Effect of Solvents:
 If the solvent has a strong magnetic anisotropy, solute-solvent
interaction will also lead to significant shift in δ value.

7. Chemical Shift Reagent:
 Chemical shift reagents are complexes of paramagnetic rare-earth
metals from lanthanide series and are used to resolve overlapping
multiplets.
 The direction of shift (upfield/downfield) depends on the metal
being used.
 Complexes of Eu, Er, Tm, Yb metals shift to downfield (larger δ
value).
CF2CF2CF3
O O
Eu3+ Eu3+
O O
3 3
Eu(dpm)3 Eu(fod)3
 Complexes of Ce, Pr, Nd, Sm, Tb, Ho metals shift to upfield

(lower δ value).

7. Chemical Shift Reagent:
 Compounds with basic pair of electrons (e.g. aldehydes, ketones,
alcohols, amines, thiols and ethers) coordinate with Eu3+.
B dpm
2B + Eu(dpm)3 Eu dpm
B dpm
 The amount of the shift depends on (i) distance between metal

(Eu3+) and the protons, (ii) concentration of the shift reagent.

Peak Integration
 An NMR spectrum can not only identify the different types of
protons present in a molecule, it can also identify the number of each
type of protons.
 The NMR spectrometer can electronically integrate the area under
each curve, which represents the relative number of that particular
type of proton in the molecule.
Relative number of
protons in benzyl
acetate is:
5:2:3

Spin-Spin Splitting
 Even in the simplest of molecules, a single proton resonance peak is
rarely observed.
 Spin-spin splitting arises because the chemically non-equivalent
protons on adjacent carbons can “sense” each other.
HA HB HA HB
R CA CB R R CA CB R
B0
R R R R
Molecule X (HA and HB with same spin) Molecule Y (HA and HB with different spin)
 Consider a situation having two different types of protons HA and HB

on adjacent carbons.
 In the same solution, in two different molecules HA might encounter
two different spin states of HB (as shown in the figures above).

Origin of Spin-Spin Splitting
HA HB HA HB
R CA CB R B0 R CA CB R
R R R R
Molecule X (HA and HB with same spin) Molecule Y (HA and HB with different spin)
 HA is said to be coupled to HB and hence its chemical shift is

influenced by the spin state of HB.
 In molecule X, spin of HB is aligned with the applied field and it adds
to the net magnetic moment. Thus HA is slightly deshielded than
normal.
 In molecule Y, HB is opposite to the applied field and it diminishes the
effect of the external field. Thus HA is slightly shielded than normal.

Origin of Spin-Spin Splitting
HA HB HA HB
R CA CB R R CA CB R
R R R R
B0
Molecule X Molecule Y
 Since in a given solution, there are approximately equal number of X

and Y-type molecules. Hence two absorptions of nearly equal intensity
are observed for HA.
 This signal pattern of HA is called a doublet.
 Likewise, HA can also take up two different spin states. Hence HA
also splits HB into another doublet.
Chemical Shift of HA Chemical Shift of HA

in X-type molecules. in Y-type molecules.
(Deshielded) (Shielded)

The Ethyl Group Splitting
 In a typical ethyl group, we have 2 different types of protons (Ha &
Hb).
Ha Hb
Ha Hb
I C C Hb
Ha Hb
Ethyl Iodide d: 3.20 1.83
 Closer look at the Ha splitting:

Ha  Each non-degenerate spin-state
arrangement of Hb gives Ha a
different chemical shift.
 Net spin +1/2 or -1/2 are more
Possible spin
states of the probable arrangements statistically.
B0 methyl protons
(Hb)  Thus, relative intensity of a
Net Spin +3/2 +1/2 -1/2 -3/2
quartet is 1:3:3:1.
Relative Intensity 1 3 3 1

The Ethyl Group Splitting
Ha Hb Ha Hb
I C C Hb
Ha Hb
Ethyl Iodide d: 3.20 1.83
 Closer look at the Hb splitting:

 Each non-degenerate spin-state
Hb
arrangement of Ha gives Hb a
different chemical shift.
 Net spin 0 is a more probable

arrangement statistically.
Possible spin
states of the
B0 methylene
protons (Ha)
 Thus, relative intensity of a triplet
Net Spin +1 0 -1 is 1:2:1.
Relative Intensity 1 2 1

Pascal’s Triangle
Singlet (s)
Doublet (d)
Triplet (t)
Quartet (q)
Quintet (quint)
Sextet (sex)
Septet (sep)
 Each type of proton “senses” the number of equivalent protons in the

adjacent carbon atom(s) and its resonance peak is split into (n+1)
peaks. This is the (n+1) rule.
 Pascals’ Triangle is a mnemonic device to extrapolate the (n+1) rule in

predicting the intensity ratios of multiplets.

Conjugate Splitting Patterns
 When a proton is surrounded by more than one type of proton in its
adjacent carbon(s), a conjugate splitting pattern is observed.
X
X HA HA, HB and HC all different types of protons.
HA and HC are expected to couple with HB and

Y HB
give a doublet pattern each.
HC
 HB splitting is more interesting, as its resonance signal is split by

both by HA and also by HC.
HB
 Such a pattern consisting of two doublets
is called a doublet of doublet (dd).
JA-B
 Which splitting is larger depends entirely

JB-C
on the chemical nature of the other
JB-C
surrounding groups.
J refers to the magnitude of splitting
Conjugate Splitting Patterns
HB
 In cases where one proton (HB) is split by 3

JA-B
other protons (HA, HC and HD), each
chemically different from itself, a doublet
of doublet of doublet (ddd) pattern is
JB-C
JB-C formed.
 Each line in the final ddd pattern would

have the same intensity, since each doublet
itself had 1:1 intensity while splitting.
JB-D
J refers to the magnitude of splitting

Nomenclature of Complex Patterns
 Names are easiest to relate to the English definition of the patterns:
HB
 We observe two triplets. Hence the name of the
JA-B
pattern is doublet of triplets (dt).
 This is observed if HA-HB coupling is stronger and
occurs first.
 Each splitting would follow its own standard
intensity pattern.
JB-C
HB
 We observe three doublets. Hence the name of
the pattern is triplet of doublets (td).
JB-C
JB-C  This is observed if HB-HC coupling is stronger and
occurs first.
 Each splitting would follow its own standard
intensity pattern.
JA-B

Coupling Constant
 Coupling constant is a quantitative measure of spin-spin splitting. It
denotes how strongly a nucleus is affected by the spin-state of its
neighbour.
 For a simple multiplet, coupling constant (J) is the difference between
the adjacent peaks of the multiplet.
 Coupling constant (J) is always measured in Hertz (Hz).

Coupling Constant
 Coupling constant is a constant. It does not change in magnitude with

change in instrument frequency.
 Increase in instrument frequency increases only the chemical shift of

the nuclei, which increases the resolution of the spectrum.
 J can be either positive or negative, but only the absolute value is
considered.
Types of Coupling Constant
 Based on the coupling partner:
 Homonuclear Coupling: Coupling between two nuclei of the same

atom.
 Heteronuclear Coupling: Coupling between two nuclei of different
atoms.
 Based on the number of intervening bonds:
 One Bond Coupling (1J): Strong coupling, mainly heteronuclear.
 Two Bond Coupling (2J): Geminal coupling, high in magnitude.
 Three Bond Coupling (3J): Vicinal coupling, lower in magnitude, but

highly significant for analysis.
 Others: Specific couplings of higher order can be extremely useful
in NMR analysis. Ex: meta coupling, allylic coupling, W-coupling.

One Bond (1J) Coupling
 Mechanism of coupling:
 Adjacent nuclei prefer to be in opposite

spin states in the ground state.
 For a typical C-H bond, two peaks are
observed in the 13C spectrum, due to the
1H 13C
two shown transitions.
1H 13C
 Some common one-bond coupling constants have been displayed below:

Two Bond (2J) Coupling
 Commonly called as geminal coupling, these are usually smaller in
magnitude than 1 bond coupling.
12C
α
1H 1H
 Some common 2 bond coupling constants:
H H H H
C C C C
H D 19F 13C
-9 to -15 Hz -9 to -15 Hz -9 to -15 Hz -9 to -15 Hz
H 19F H
C C C
H 19F 31P
-9 to -15 Hz -9 to -15 Hz -9 to -15 Hz

Variation in 2J Coupling
 Geminal coupling increases in magnitude as the bond angle (α)
decreases, due to higher electron spin correlation.
H H
Bu
O
H H H
H H H H
α = 120° α = 118° α = 109° α = 107°

2J
H-H = 0-2 Hz
2J
H-H = 5 Hz
2J
H-H = 12-18
2J
H-H = 17.5 Hz
Hz

Three Bond (3J) Coupling
 Commonly called as vicinal coupling, these usually follow the (n+1) rule
in simple aliphatic hydrocarbon chains.
 Nuclear and electronic spin interactions carry the spin information

from one hydrogen to its neighbour.
This weak sideways overlap is responsible

for transfer of spin information.
Dihedral Angle = 0°
This C-C bond is almost orthogonal to the

C-H bonds. So they can not interact.
 As a result, the best overlap occurs when the C-H bonds are at a
dihedral angle of 0°.

 The magnitude of vicinal coupling is directly related to the dihedral
angle between the C-H bonds in question.
 The Karplus equation relates dihedral angle to coupling constant
between two vicinal hydrogen nuclei.
Dihedral Angle = 0° or 180°

Best Overlap; Highest Coupling Constant
Dihedral Angle = 90°

Worst Overlap; Lowest
Coupling Constant
(End-on view)

 cis/trans alkenes:
R R R Hb
Ha Hb Ha R
3J = 11-18 Hz 3J = 6-15 Hz
ab ab
 Cyclohexane systems:
Ha Ha Y
Y Y Ha
X Hb Hb
Hb X X
Dihedral Angle = 180° Dihedral Angle = 60° Dihedral Angle = 60°
3J
ab = 2-5 Hz
3J
ab = 2-6 Hz
3J
ab = 10-14 Hz
 Cyclopropane/Epoxide Systems: Jcis > Jtrans (unlike in alkenes)

Hb R Hb R
Ha Ha Ha Ha
O O
R Hb R Hb
Hc Hc Hc Hc
3J 3J = 4-5 Hz
ab = 2-9 Hz
3J = 6-12 Hz 3J
ab ab ab = 2-4 Hz
2J
ac = 5-6 Hz
2J
ac = 3-9 Hz

Long Range Coupling
 Very rarely, but often significantly, coupling takes place between two
atoms separated by four bonds or more (nJ; n≥4).
 The common systems where this is exhibited are: allylic systems,

rigid bicyclic systems and aromatic rings.
 Since these couplings are observed through a large number of bonds,
a highly specific stereochemical arrangement is essential.
R R X
Me
Ha X Ha
Me
Hb R Hb R
R
X Ha Hb
Some common systems where 4-bond coupling is observed

Allylic & Propargylic Coupling
 Here the spin information is transferred through interaction between
the C-H σ-orbital and the olefin π-orbitals.
H H
R
H H
R R R
C-H σ-orbital parallel to π-orbital. C-H σ-orbital orthogonal to π-orbital.

Maximum overlap; 4J = max Minimum overlap; 4J ≈ 0
 In propargylic coupling, the C-H σ-orbital is always in partial overlap

with at least one set of π-orbitals. So, propargylic coupling (2-4 Hz),
as a weighted average from all possible conformations is higher than
allylic coupling (0-3 Hz).
R
H

W-type Coupling
 Long range coupling in compounds not having π-bonds is rare, as π-
orbitals serve as the most effective means of transferring spin
information.
 But in some cyclic systems, it is observed where the two C-H bonds
in question are held in position by the rigidity of the system.
 The two bonds forming a W-type orientation gives rise to very small,
but highly characteristic and sometimes very significant coupling.
H H
H O
H H Bu
H H
H H
H
4J = 1.0 Hz 4J = 7.0 Hz 4J = 1.4 Hz

Practice Problems
 Molecular formula: C3H7I
1 3
I
2

Practice Problems
 Molecular formula: C3H6O O
 IR: 1720 cm-1

Practice Problems
 Molecular formula: C4H8O
 IR: 1718 cm-1
O
4
1 2
3

Practice Problems
 IR: 1718 cm-1
O

Practice Problems
 Molecular formula: C5H10O2
 IR: 1740 cm-1
O

Practice Problems
 IR: 1742 cm-1
O
2 3 6
O 5 O
1 4 7

Practice Problems
 IR: 2971, 1721, 1718 cm-1
O O
HO

Practice Problems
 Molecular formula: C5H9ClO2
 IR: 1745 cm-1
Cl O

Practice Problems
 Molecular formula: C5H9ClO2
 IR: 1800 cm-1
Cl O

Practice Problems
 IR: 1740 cm-1
6
O
3
1 2 O 5 6
4

Practice Problems
 IR: 1690, 1620 cm-1
O 5
1
2 3 4 6

Practice Problems
 IR: 1685, 1622 cm-1

Practice Problems
O
 IR: 1720 cm-1 O

Practice Problems
 Molecular formula: C14H12O2 O
 IR: 1720 cm-1 O

Practice Problems
 IR: 1686 cm-1

Practice Problems
 IR: 1685 cm-1

Practice Problems
 Molecular formula: C10H12O3 O
 IR: 1720 cm-1 O
O

Practice Problems
 IR: 1715 cm-1
OMe

Practice Problems
 IR: 1720 cm-1

Practice Problems
 IR: 1693 cm-1

Different Functional Groups
Alkanes
Chemical Shifts:
R-CH3 0.7-1.3 ppm Often come as tall singlet/ doublet/
triplet.
R-CH2-R 1.2-1.4 ppm Unresolvable multiplets.
R3CH 1.2-1.4 ppm Unresolvable multiplets.
Coupling Behavior:
-CH-CH- 3J = 5-6 Hz

Alkenes
Chemical Shifts:
C=C-H 4.5-6.5 ppm Often come as d/ dd/ ddd.
C=C-C-H 1.6-2.6 ppm Allylic H’s are also deshielded by

anisotropy of double bond.
Coupling Behavior:
H-C=C-H 3J = 12-18 Hz
trans
3J
cis = 6-15 Hz
H
2J = 0-3 Hz
C C
H
4J = 0-3 Hz
C C C H
H

Aromatic Compounds
Chemical Shifts:
Often come as d/ dd/ ddd for
H 6.5-8.0 ppm
substituted aromatic systems.
CH2 2.3-2.7 ppm Effect of anisotropic effect is smaller

because these protons are distant.
Coupling Behavior:
3J = 7-10 Hz
ortho
H 4J
meta = 2-3 Hz
H 5J
para = 0-1 Hz

Aromatic Compounds
 para-Disubstituted Rings:
 EDG’s increases electron density
of the ring. Peaks appear in
upfield.
 EWG’s decreases electron
density from the ring. Peaks
appear in downfield.
 NMR spectrum becomes complex when both the substituents are

different. In high resolution NMR instrument these peaks will appear
as four distorted triplets.
OMe
Ha Ha'
Hb Hb'
Jab ¹ Jab'
Ja'b' ¹ Ja'b

Aromatic Compounds
 para-Disubstituted Rings:
 In low resolution instrument these protons may appear as two
doublets

Aromatic Compounds
 ortho-Disubstituted Rings:
 When two substituents are same, spectrum

shows four distorted triplets like para-
disubstituted rings.
 When two substituents are different, spectrum becomes more

complex than a symmetric compound.

Aromatic Compounds
 meta-Disubstituted Rings:

Aromatic Compounds
 meta-Disubstituted Rings:
d 10.15
OH
d 7.34 H H d 7.76
d 7.39 H NO2
H
d 7.82

Aromatic Compounds
 Other Substituted Rings:
Low resolution
High resolution

Aromatic Compounds
 Other Substituted Rings:

Practice Problems
 Molecular formula: C7H5NO3
 IR: 2860, 1705, 1550, 1330 cm-1
O 7 H
1
6 2
3
5 NO2
4

Practice Problems
 Molecular formula: C7H7I
 IR: 3050, 2900, 2860 cm-1 7
CH3
1
6 2
5 3 I
4

Practice Problems
 Molecular formula: C9H6N2O3
 IR: 3260, 2910, 2870, 1520, 1330 cm-1
NO2
5 4
10
6 3
7 2
8 9 N
OH 1

Heteroaromatic Compounds
 Coupling in Heteroaromatic Systems:
3J 1.6-2.0 Hz
H b' Hb αβ
4J 0.3-0.8 Hz
αβ’
4J 1.3-1.8 Hz
Ha' Ha αα’
O 3J
ββ’ 3.2-3.8 Hz
3J 4.0-6.0 Hz
ab
Hc 4J 0.0-2.5 Hz
ac
Hd Hb 5J 0.0-2.5 Hz
ad
4J < 1.0 Hz
ae
He N Ha 3J 7.0-9.0 Hz
bc
4J 0.5-2.0 Hz
bd

Heteroaromatic Compounds
 Coupling in Heteroaromatic Systems:
Hb Hc
Ha O CH2OH
Hc
Ha Hb
Hd N CH3
Alkynes
Chemical Shifts:
Due to anisotropic effect acetylenic
C C H ~ 1.9 ppm
protons appear in so upfield.
Protons next to a triple bond also get

C C CH 1.6-2.6 ppm affected because of magnetic
anisotropy.
Coupling Behavior:
4J = 2-3 Hz
H C C C H
2
Alkyl Halides
Chemical Shifts:
-CH-I 2.0-4.0 ppm Deshielding effect is due to
electronegativity of the halogen atoms.
-CH-Br 2.7-4.1 ppm
-CH-Cl 3.1-4.1 ppm
-CH-F 4.2-4.8 ppm
Coupling Behavior:
-CH-F 2J = 50 Hz
3J = 20 Hz
-CH-CF-
Alcohols
Chemical Shifts: Position of hydroxyl group depends on
-C-OH 0.5-5.0 ppm concentration, solvent and
temperature. The may be broadened.
α-Protons are deshielded due to

-CH-OH 3.2-3.8 ppm
electronegativity of oxygen atom.
Coupling Behavior:
-CH-OH 3J = 5 Hz
Ethers
Chemical Shifts:
These protons get deshielded due to
R-O-CH- 3.2-3.8 ppm
electronegativity of oxygen.
Amines
Chemical Shifts:
Variable chemical shift depending on
R-N-H 0.5-4.0 ppm
temperature.
-CH-N- 2.0-2.9 ppm These protons get deshielded due to

electronegativity of nitrogen.
N H 3.0-5.0 ppm These protons get deshielded due to
anisotropy of the ring.
Nitriles
Chemical Shifts:
These protons are shielded due to
-CH-CΞN 2.1-3.0 ppm
anisotropy of nitrile group.
Aldehydes
Chemical Shifts:
Aldehyde protons are so deshielded
R-CHO 9.0-10.0 ppm
because of anisotropic effect of
C=O.
R-CH-CHO 2.1-2.4 ppm α-protons appear in much upfield
range because they are much distant.
Coupling Behavior:
-CH-CHO 3J = 1-3 Hz
Ketones
Chemical Shifts:
α-protons are deshielded because of
R-CH-CO-R 2.1-2.4 ppm
anisotropic effect of C=O.
Esters
Chemical Shifts:
-CH2-CO-OR 2.1-2.5 ppm
These protons are deshielded due to

R-CO-OCH2- 3.5-4.8 ppm
electronegativity of oxygen.
Carboxylic Acids
Chemical Shifts:
Characteristic peak for carboxylic
R-COO-H 11.0-12.0 ppm
acids.
-CH2-COOH 2.1-2.5 ppm
Amides
Chemical Shifts:
Variable chemical shift value, depends on
R-CO-NH- 5.0-9.0 ppm
temperature, concentration, solvent.
-CH-CONH- 5.0-9.0 ppm
R-CO-N-CH2- 2.2-2.9 ppm Due to electronegativity of nitrogen.
Nitroalkanes
Chemical Shifts:
-CH-NO2 4.1-4.4 ppm Deshielded by nitro group.
Chemical Equivalence
 If any element of symmetry renders two or more nuclei equivalent by
symmetry, then they are said to be chemically equivalent.
 In most cases chemically equivalent nuclei resonate at the same

frequency, do not split each other and give a single signal in NMR.
O Cl
O
H H H
H H
H3C H H
H H
H H
Cl
H CH3
Plane as well as Plane as well as
axis of symmetry axis of symmetry
Axis of symmetry
All protons in each of the individual groups are chemically equivalent due to symmetry
Magnetic Equivalence
 A group of nuclei are magnetically equivalent when their magnetic
environments, including their coupling interactions are identical.
 Magnetically equivalent nuclei must have the same chemical shift.
 Magnetically equivalent nuclei must have equal coupling constants with

every other nuclei in the molecule.
 Due to free rotation of the C-C bonds, every proton has

O
the same chemical shift and the same coupling constant
H H
H
with all other nuclei in the molecule.
H
H H
 Hence all 6 protons are chemically as well as
Plane as well as
axis of symmetry magnetically equivalent.
Magnetic Inequivalence
X
HA HA
HB HB
Y
 HA−HB(ortho) coupling ≠ HA−HB(para) coupling.
 Even though the two HB nuclei are chemically equivalent, they do not
have the same coupling constants with the same HA nuclei.
 Thus even though the two HA nuclei (and the two HB nuclei) are
chemically equivalent, they are magnetically nonequivalent.
 Such molecules produce complex splitting patterns, giving rise to a

second order spectrum (will be defined later).
Magnetic Inequivalence
Jtrans
HA HB  (HA, HB) & (FA, FB) are both chemically
Jcis
equivalent, but magnetically nonequivalent
FA FB pairs.
H3C CH2 CH2 Cl

C B A
CH3
Janti
 HA & HB are both chemically equivalent, but
Jsyn
HA HA magnetically nonequivalent.
HB HB
Cl
If conformation is locked
 Geminal groups (protons and methyl groups mainly) are the subjects of
interest in terms of their stereochemical relationship.
Topicity
 Homotopic groups:
 Interchangeable by rotation or reflectional symmetry elements.
 They give only a single signal in NMR.
 If two homotopic groups in a molecule are substituted separately,

the same molecule will be obtained in both cases.
HB
X
C2, s Homotopic methyls
X
HA
H3 C CH3
HA and HB interchangeable
both by a C2 axis as well
as by a mirror plane. OH OH
Topicity
 Enantiotopic groups:
 Interchangeable by only reflectional symmetry elements.
 They give only a single signal in NMR, unless placed in some

chiral environment.
 If two enantiotopic groups in a molecule are substituted
separately, different enantiomers will be obtained in the two
cases.
HB H3C CH3
X
s HB
Enantiotopic protons
Y HA
HA
HA and HB interchangeable OH OH
only by a mirror plane.
Topicity
 Diastereotopic groups:
 Not interchangeable by any symmetry elements.
 They always give different signals in NMR and couple differently

with other magnetically active nuclei.
 If two diastereotopic groups in a molecule are substituted

separately, different diastereomers will be obtained in the two
cases.
HB Diastereotopic methyls
X
Y*
HA H 3C CH3
HB
H3C Diastereotopic protons
Y* contains chiral group(s) HA
HA and HB not interchangeable OH OH

by any symmetry element.
Order of an NMR Spectrum
 An NMR spectrum is said to be of first order if:
 It follows the (n+1) rule for splitting patterns and relative

intensities of the peaks.
 If coupling constants for multiplets can be calculated by simple
difference between the adjacent peaks.
 If all chemically equivalent nuclei couple equally with all other
nuclei in the molecule.
 (Δν/J) ≥ 7 ; where:
• Δν is the difference in chemical
shift between two groups (in Hertz)
• J is the coupling constant between
the two groups (in Hertz)
Second Order Spectrum
 An NMR spectrum is said to be of second order (or non-first order)
if (Δν/J) value is less than 7.
 Such situations arise due to the presence of magnetically
nonequivalent nuclei.
 Second order spectra are much more difficult to analyze: splitting
patterns do not correspond to the (n+1) rule, coupling constants are
not uniform.
 Normally, the presence of diastereotopic groups lead to second order
spectra.
 With spectrometers of higher frequency, chemical shifts become
more resolved (Δν increases), but J values remain the same. (Δν/J)
increases overall.
 Hence with spectrometers of higher frequency, second order effects
begin to disappear.
Spin System Notation
 Pople Notation:
 Each chemically different proton is assigned a capital alphabet;

A, B, C…
 Protons of widely different chemical shifts are assigned
alphabets which are far apart: A, B, C with X, Y, Z.
 Protons of very close chemical shifts are assigned alphabets
which are very close together: A, B, C with each other.
 So, an AX system is of first-order and an AB system is of
second order.
 So, an AMX system denotes a 3 proton system where each is
very different from the others.
CH2 CH2 O Cl CH2 CH2 O
A2X2 O A2B2
AX Systems
 Relatively simple to analyze.
60 MHz 1H NMR of phenylethyl acetate
AB Systems
C C
H H
 Much more difficult to analyze and

patterns change upon change of the
(Δν/J) value.
 With lowering of the (Δν/J) value,

an AX system changes to an AB
system and ultimately the two
protons in question, become
equivalent (A2 system).
AB Quartets
 In a typical AB quartet with low (Δν/J)

value, the outer peaks are much smaller in
intensity than the inner peaks.
 Clearly, at higher spectrometer frequencies,

an AB quartet gets resolved into two
doublets.
 Often difficult to distinguish from a normal

quartet, but an AB quartet must always
integrate to at least 2 protons.
AB Quartets
SMe O
H
HB HA
 In the above compound, HA and HB are diastereotopic and have very

close chemical shifts.
 The complex pattern seen above is observed at δ = 2.64, which is
actually an AB quartet, further split as a doublet of doublet.
 The AB quartet is for the two protons HA and HB and they further
couple with the two adjacent protons to split into another dd.
 Intensity of the AB quartet is not in the ratio 1:3:3:1.
 Coupling constants J and A are not equal.
A2B2 Systems
60 MHz
500
MHz
A2B2 Systems
60 MHz
500
MHz
AMX Systems
 When 3 protons of widely varying chemical shifts are present, it is
denoted by three widely spaced letters in the alphabet series:
A,M,X.
 Jcis > Jtrans: in accordance with small rings as discussed earlier.
AMX Systems
 HC is most deshielded as it is directly attached to an oxygen bearing

carbon.
 Jtrans > Jcis: in accordance with olefins as discussed earlier.
Home Work
 Assign aromatic protons of methyl salicylate using chemical shift
values and splitting pattern of given spectrum:
Home Work
 1H spectrum was obtained from dimethyl cyclopropanedicarboxy-
late. Is it a cis or trans isomer? [CDCl3, 400 MHz, 298 K]
Home Work
 Derive the structure of a compound using following NMR spectrum.
Molecular formula C5H8O2. [CDCl3, 90 MHz, 298 K]
Home Work
 Predict the structure using following NMR spectrum. Molecular
formula C5H6O. [CDCl3, 90 MHz, 298 K]
Home Work
 Predict the structure using following NMR spectrum. Molecular
formula C7H7NO. [CDCl3, 90 MHz, 298 K]

NMR

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NMR

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Nuclear Magnetic Resonance

CH-521 Course on Interpretative Molecular Spectroscopy; Course Instructor: Krishna P. Kaliappan 1

 In absence of any external magnetic field, all nuclear spin states

CH-521 Course on Interpretative Molecular Spectroscopy; Course Instructor: Krishna P. Kaliappan 2

 Most notably, two of the most abundant nuclei in organic compounds

CH-521 Course on Interpretative Molecular Spectroscopy; Course Instructor: Krishna P. Kaliappan 3

S N Spin Opposed System:

CH-521 Course on Interpretative Molecular Spectroscopy; Course Instructor: Krishna P. Kaliappan 4

No Field Applied Field No Field Applied Field

 γ is the ratio between the magnetic moment and angular momentum of

 Gyromagnetic ratio is constant for a given nucleus and hence the

 Angular momentum is quantized in the form of (h/2π) units, eqn 1

 Frequency of the absorbed energy can be expressed as:

CH-521 Course on Interpretative Molecular Spectroscopy; Course Instructor: Krishna P. Kaliappan 6

 If the correct value of γ is substituted, we find that for an applied

Resonating frequencies of a few common nuclei

CH-521 Course on Interpretative Molecular Spectroscopy; Course Instructor: Krishna P. Kaliappan 7

 Energy difference is directly proportional to the magnetic field

CH-521 Course on Interpretative Molecular Spectroscopy; Course Instructor: Krishna P. Kaliappan 8

 Resonance is accompanied by a change in spin of the nucleus.

 This excess population of 9 electrons is extremely important as it is

 With increase in instrument frequency, the energy gap between the

 At extremely high instrument frequencies, population in each level

CH-521 Course on Interpretative Molecular Spectroscopy; Course Instructor: Krishna P. Kaliappan 11

 Modern NMR spectrometers all contain

 The liquid helium chamber in turn, is

 Superconducting magnets of 400 MHz

CH-521 Course on Interpretative Molecular Spectroscopy; Course Instructor: Krishna P. Kaliappan 12

A Pulse Frequency content of the pulse

 A pulse excites all target nuclei in the molecule.

 Since a variety of different types of protons were excited, radiations

 Hence the FID is a time-domain signal.

CH-521 Course on Interpretative Molecular Spectroscopy; Course Instructor: Krishna P. Kaliappan 14

CH-521 Course on Interpretative Molecular Spectroscopy; Course Instructor: Krishna P. Kaliappan 15

 Hence the Signal:Noise ratio can be vastly improved by increasing the

CH-521 Course on Interpretative Molecular Spectroscopy; Course Instructor: Krishna P. Kaliappan 16

 Multiple iterations can be given on the sample in additive manner to

 This helps in increasing sensitivity towards less abundant nuclei,

CH-521 Course on Interpretative Molecular Spectroscopy; Course Instructor: Krishna P. Kaliappan 17

 Spinning electrons create an induced magnetic field that opposes

 Nuclei are surrounded by electrons that create a shield over them

Beffective = Bexternal - Binduced

 Changes in distribution of electrons around nuclei affects (i) net

 When a nucleus is covered with electronic cloud around it, it is

CH-521 Course on Interpretative Molecular Spectroscopy; Course Instructor: Krishna P. Kaliappan 18

 Chemical shifts are expressed by δ (Delta), which are defined as

 Measurement of precessional frequencies of a group of nuclei is not

 Generally the difference in frequencies are measured with respect

 Most common internal standard for 1H and 13C is tetramethylsilane

CH-521 Course on Interpretative Molecular Spectroscopy; Course Instructor: Krishna P. Kaliappan 19

Where δX is the chemical shift (in ppm).

 Signals having higher δ values (more deshielded) are called

CH-521 Course on Interpretative Molecular Spectroscopy; Course Instructor: Krishna P. Kaliappan 20

 Should be chemically inert.

 Should have low boiling point, so that samples could be recovered.

 Should be soluble in most organic solvents.

 TMS is commonly used for 1H, 13C NMR experiments.

 CFCl3 is used for 19F NMR experiments.

CH-521 Course on Interpretative Molecular Spectroscopy; Course Instructor: Krishna P. Kaliappan 21

 What could be the factors controlling chemical shift values of

CH-521 Course on Interpretative Molecular Spectroscopy; Course Instructor: Krishna P. Kaliappan 22

 Electron withdrawing groups attached to a carbon, withdraws valence

Compound CH3F CH3OH CH3Cl CH3Br CH3I CH4 (CH3)4Si