07-Sep-16

BondStretchingFrequencies:Hydrogen
BondStretchingFrequencies:
Hydrogen
Increase (cm-1)

Decrease (cm-1)

07-Sep-16

NUCLEAR MAGNETIC RESONANCE (NMR)

References:
Chapter 3, Introduction to
spectroscopy
D. Pavia, G. Lampman, G. Kriz
Chapter 1, Fundamentals of Molecular
spectroscopy C
spectroscopy,
C.N.
N Banwell and E
E.M.
M
McCash

HistoryofNMR
The Zeeman effect , is the effect of splitting a spectral line into several
components in the presence of a static magnetic field, and it is very
important in applications such as nuclear magnetic resonance
spectroscopy,
p
py electron spin
p resonance spectroscopy,
p
py magnetic
g
resonance
imaging (MRI) and Mssbauer spectroscopy

for his contribution to the development of

the molecular ray method and his discovery
of the magnetic moment of the proton".

Otto Stern
Nobel prize in Physics 1943
Becker, E.D., Anal. Chem. 1993, 65, 295.

07-Sep-16

NMR
1938

Isidor Rabi

1945

"forhisresonancemethodfor
recordingthemagnetic
propertiesofatomicnuclei"

Nobel prize in
Physics 1944

In 1945 two
t o groups
gro ps of physicists,
ph sicists one at Stanford,
Stanford
the other at Harvard, first reported the detection
of NMR signals in condensed matter. The
Harvard group led by Edward Purcell discovered
the phenomenon in solid paraffin; the Stanford
group, under the wing of Felix Bloch, found it in
liquid water. Purcell and Bloch shared the 1952
Nobel Prize in Physics.

Edward Mills Purcell

fortheirdiscoveryofnew
methodsfornuclearmagnetic
precisionmeasurementsand
discoveriesinconnection
therewith

Nobel prize in
Physics 1952

Felix Bloch

Future of NMR and Nobel prize

Ernst spoke of the scientific areas that he thinks
could win the Nobel prize in the future. He
described functional MRI as an exciting field. 'You
You
can learn so much about brain function from
magnetic resonance,' he enthuses. He believes that
the chemistry of biological processes is a hot area
to look out for, but also thinks 'there could be more
prizes for nano-devices with chemical functions' in
the future as well.

http://www.rsc.org/chemistryworld/News/2010/July/13071002.asp

07-Sep-16

Introduction
Important tool for structural elucidation
Nucleus and electrons are tiny charged particle and their posses tiny
magnetic pole
Reversal of dipole consequent with the reversal of nuclei spin interact with
the applied magnetic field (Bo)
The spin reversal associates with the amount of energy absorbed or emitted.
The amount of energy absorbed for the spin reversal is measured in NMR
Radio frequency region: 3x106- 3x106 Hz (10 m 1 cm)
Energy change during the reversal of spin is of the order EE=10
10310
10 J/mol
For example, number of each distinct types (chemically inequivalent) of
hydrogen nuclei and the nature of the immediate environment of each type
are obtained
7

Nuclear Spin States (I)

Atomic nuclei have spin (like electrons) and behave as if they were spinning
Atomic molecules having odd mass, odd at. no. or both has a quantized
spin angular momentum and a magnetic moment
Nuclei with even atomic number and mass value has spin value of zero
For each nuclei, the allowed spin state is 2I+1 and it varies from I to +I

Element:

1 H
1

Nuclear Spin

1H

1/2

12

6C

13

6C

14

7N

16

8O

17

8O

19

9F

31 P
15

1/2

5/2

1/2

1/2

Quantum No.(I)
No (I)
No. of Spin

States (l to l)
For example,

1 H,
1
2

1H,

2X + 1 = 2 spin states varies from -1/2 to +1/2

2X 1 + 1 = 3 spin states varies from -1, 0, 1

07-Sep-16

Nuclear Magnetic moments

Allowed spin states for Proton

-1/2 (opposed)
Bo

No field

+1/2 (aligned)

Arrangements in Bar magnet

In the absence of magnetic field, all the spin

states are equivalent in energy (degenerate)
In the presence of Bo the energy of the spin is
aligned or opposed (see the diagram)
For aligned spin state with respect to Bo, their
energy is lower and if opposed the energy is
higher like in bar magnet

Absorption Energy
-1/2

-1/2
h
No field

Bo
+1/2

+1/2

Upon
U
absorption
b
ti off energy, the
th spin
i state
t t off nuclei
l i is
i changed
h
d with
ith respectt
to applied magnetic field. This can be written as
Eabs = E (-1/2) E (+1/2) = h
-1/2

E = f(Bo) = h
No field

Therefore,
energy
difference is a function
off the
th strength
t
th off the
th
applied magnetic field
Stronger the Bo greater
is the separation of spin
states
+1/2
Bo

10

07-Sep-16

Absorption Energy
Energy absorbed is a quantized process and it is the difference between two
states
E abs = E (-1/2) E (+1/2) = h
E = f(Bo)
Magnitude of separation also depends on the particular nuclei
Each
E h Nucleus
N l
h
has
diff
difference
i the
in
th ratio
ti off magnetic
ti momentt to
t angular
l
momentum due to the different charge to mass ratio known as magnetogyric
ratio ()
E = f(Bo); = magnetogyric ratio
E = f( Bo) = h
E = f( Bo) = h
Since the angular momentum of the nucleus is quantized in units of h/2 then
energy
E = (h/2)(Bo) = h;
= ( / 2)Bo
For 1 tesla of magnetic field strength
= (267.53 x 106 / 2 x 3.14)1
= 42.6 MHz
Higher the field strength greater is the energy separation and
frequency of absorption
11

Frequenciesandfieldstrength

12

07-Sep-16

PopulationsDensitiesNuclearSpinStates

(For 60 MHz)

13

Diamagneticshielding(or)diamagneticanisotropy

Chemical shift:

= 106 x [obs ref/ obs]

Diamagnetic anisotropy the diamagnetic

shielding of a nucleus caused by the circulation
of valence electrons generates local diamagnetic
current which generates the induced magnetic
field (B) opposes applied magnetic field (Bo)
Thus,
Thus in a molecule,
molecule hydrocarbon,
hydrocarbon each proton
is shielded from Bo
Greater the number of electrons around the
nucleus, greater the induced magnetic field (B)
which shields the nucleus from Bo
Beff =Bo(1-)
= shielding constant
The effect of shielding constant is small
Instead, difference between the resonance
frequency
q
y of the nucleus in the unknown(
( obs)
and the reference of the standard (ref) is taken.
Generally reference value is taken as zero
Since this difference is small the value is
multiplied by a million (106).
The frequency depends on strength of
magnetic field
Incorporating these fact the new parameter
14
chemical shift ( ) is used to report the values

07-Sep-16

Chemical shift
For a given spectrophotometer frequency, the chemical shift observed is equal
to the difference in the resonance frequency.
This means one has to expect different frequency for the same compound if we
measure in two different spectrophotometer operating varying Bo and hence
frequency
For example,
p ,p
proton in methyl
y bromide resonates at 162 Hz in 60MHz,,
whereas the same appear at 270 Hz under 100 MHz instrument
To make it uniform the observed resonance, the chemical shift () values are
always related to spectrophotometer frequency ()
Thus
For methyl bromide

= 106 x [/ spectrophotometer frequency]

= 162/60 = 2.70 ppm = 270/100

For proton,
15

SymmetryandChemicalEquivalence

16

07-Sep-16

IntegralandIntegration

Benzyl acetate in 60 MHz NMR FT - NMR

17

IntegralandIntegration

Benzyl acetate in 300 MHz NMR FT - NMR

18

07-Sep-16

ChemicalShift

19

DiamagneticShielding
Diamagnetic shielding depends on the following factors
Electro-negativity of the adjacent atoms
Hybridization effects
acidic and exchangeable protons; Hydrogen bonding

El t
Electro-negativity
ti it off the
th adjacent
dj
t atoms
t

20

10

07-Sep-16

Spin Spinsplittingintwo
differentNMRactivenuclei

21

Spin Spin splitting between two different NMR active nuclei

Stick first to systems with all of the nuclei having I = 1/2
(N.B. When we have two chemically different nuclei, e.g. P and F, they will come to
resonance at completely different parts of the spectrum generally NMR
spectrometer to scan one type of nucleus at a time).

AX
Both

31P

and

(e.g. a molecule containing the unit >P-F)

19F

have I = 1/2, so each nucleus will "see" the other in two

possible orientations, and each will therefore absorb at two different energies
(a doublet).
What are the intensities of the two components of this doublet?
Energy gap between the two energy levels is very small therefore (Boltzmann
distribution) very nearly as many nuclei in the (slightly) higher energy level
than in the (slightly) lower energy level. Thus each nucleus sees approx.
equal numbers of neighbours in the two possible alignments.
22

11

07-Sep-16

Hence both of the 31P and the 19F n.m.r. spectra will comprise doublets - with each
doublet having an intensity ratio 1:1.
spin-spin splitting
31P

spectrum:

(magnitude given by COUPLING CONSTANT,

J - measured in Hz, i.e. a frequency)

This one will be

1J
PF i.e. through one bond.

centre of resonance

1J
PF

The 19F resonance will look exactly the same

- with the same coupling constant (this is a
mutual effect)
centre of resonance
19F resonance

23

Note:
1. Spin-spin coupling can be transmitted through >1 bond, giving
coupling constants which generally decrease with increased number of
intervening bonds, i.e.
1J
AX

>

2J
AX

>

3J
AX

....... etc

(A, X = general symbols for two magnetically distinct nuclei)

Coupling increases with increasing S orbital character
J / Hz = k x %s(A) x %s(x)

where, k is constant

2. Mechanism of spin-spin coupling is that the effects are transmitted

via intervening electrons
electrons.

Suppose that we have >2 nuclei interacting (still restricted to

all I = 1/2).

24

12

07-Sep-16

AX2

e.g. the 31P resonance in a -PF2 unit.

The F (X) nuclei can have their spins arranged as follows:

1 : 2 : 1
The two bracketted arrangements will have the same effects on the P (A)
nucleus. Thus the A nucleus will be in THREE possible environments, and
so the A resonance will be a TRIPLET. Also, one of the environments is
twice as likely as the other two (which are equal), so the intensities of
the triplet will be
Hence the A resonance in AX2, e.g
e g P in -PF
PF2 will be:
(1JPF) 1JAX

1J
1
AX ( JPF)

In this system the X (F) resonance

will again be a DOUBLET due to the two possible orientations
of A (P).
25

AX3

Again consider A resonance,

e.g. 31P resonance of the molecule PF3.

The A (P) nucleus will see the X (F) nuclei in the following orientations:

EIGHT possible arrangements - two sets of three (bracketted) equivalent.

Thus A resonance will be a QUARTET, with relative intensities 1 : 3 : 3 : 1.
The 31P resonance in PF3 will therefore be:
1J
PF

1J
PF

1J
PF

26

13

07-Sep-16

Time to give a general rule for the appearance of the A resonance in any
AXn system (where all nuclei have I = 1/2).
First note trends so far:
First,
n

system

no. of lines

intensities

1 (singlet)

AX

2 (doublet)

1:1

AX2

3 (triplet)

AX3

4 (quartet)

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

i.e. A resonance has (2nI + 1) lines (remember here I = 1/2 for X).
Intensities - these can be expressed in general using
PASCAL'S TRIANGLE.
27

A
AX

singlet

1:1

doublet

AX2

1:2:1

triplet

AX3

1:3:3:1

quartet

AX4

1:4:6:4:1

q intet
quintet

AX5

1 : 5 :10 :10 : 5 : 1

sextet

AX6

1 : 6 : 15 : 20 : 15 : 6 : 1

septet

AX7

etc.

Each element formed by taking sum of elements on row above to

left and right, with 1's at the ends.
Mathematically - it is the set of coefficients for the binomial
expansion of (x + y), i.e. (x + y)n.

28

14

07-Sep-16

Spin Spin splitting between three different NMR active nuclei

Now we can predict A resonance for any AXn
but what if there are >2 different types of nucleus. Many possibilities!!
Let us take some examples

AMX

i.e. a nucleus interacting with one each of two

different nuclei, e.g. the fluorine in a unit:
M
A
X
H
P
F

Let us first look at 19F-NMR

Remember that spin-spin coupling decreases with increased number of
intervening bonds.
Hence the fluorine couples most strongly to P, giving a doublet. But for
each possible orientation of the P nucleus there will also be two
different orientations of the H, so each component of the original
doublet will also be split into a doublet - giving a DOUBLET OF
DOUBLETS:

29

2J
FH

1J
PF

F resonance
This doublet of doublets is characteristic of an AMX system.
We can work out the P and H resonances similarly.
First the P resonance - difficulty here is that there are two "one-bond"
coupling constants. Which is the bigger?

F
30

15

07-Sep-16

Remember that coupling occurs via intervening electrons.

F has more electrons than H, therefore

1J
PF

>

1J
PH
1J
PH

Therefore P resonance is split into

a doublet by F, then
into a doublet by H, again giving a
doublet of doublets:

1J
PF

P resonance
2J
FH

1J
PH

For the H resonance, the argument

is exactly the same as for the F,
giving:
H resonance

AMX2

31

e.g. molecule HPF2.

2J
FH

1J
PF

F resonance
Si il to
Similar
t AMX,
AMX doublet
d bl t off doublets
d bl t is
i expected
t d for
f an AMX2 system.
t

32

16

07-Sep-16

1J
PH

2J
FH

The H resonance, however, will be a

DOUBLET OF TRIPLETS
- major splitting by one P, minor
splitting by two F's:

H resonance

Consider P resonance.
By same arguments,
arguments this will
be a TRIPLET OF DOUBLETS
i.e. major splitting by two F's
to
give
triplet,
further
(smaller) splitting by H into
doublet.

1J
PF

P resonance
1J
PH

33

NMR and Geometry of AXn

Consider the following PFn spectra (31P and 19F NMR) and arrive at the value of
n and hence the geometry of the molecule. The spectra below were recorded
in DMSO-d6.

31P

NMR

http://fluorine.ch.man.ac.uk/research/nmr_terms.php

19F

NMR

34

17

07-Sep-16

KPF6
The

31P

NMR spectrum consists of a septet, indicating that six fluorines are

present in the nearest environment (n= 6)

All the six fluorines are equivalent
Hence the formulation should be in the [PF6]- anion
The formulation can be further ascertained by looking at the

19F

NMR which

shows doublet.
Therefore the structure should be octahedral [PF6]-, which is supported by VSEPR
The separation between any adjacent pair of peaks is the P-F coupling, in this

case 711 Hz. Since all six fluorine nuclei are equivalent they couple to just the
give a doublet, again
g
separated byy 711 Hz.
phosphorus nucleus to g
Thus the two nuclei are said to exhibit mutual coupling, that is they couple to each

other in the same way. The PF coupling constant labeled as 1J(PF) [where the
superscript 1 refers to the 1 bond between the P and F nuclei] is 711 Hz.
Note: coupling constants are always quoted in Hz (which is independent of the
spectrometer frequency) not ppm!!!

35

NMRofnucleiwhereI>1/2
There are three main factors that affect the ease of observing nuclei
Receptivity (sensitivity)
line-width
chemical shift dispersion
Receptivity (sensitivity)
Different nuclei have different receptivities, 1H being the most sensitive stable
nucleus with 19F following closely behind.
The effective receptivity is a product of the nucleus' inherent receptivity and
its natural abundance
For example 3He has an inherent receptivity 0.44 times that of proton but has
such a low natural abundance that it is all but unobservable; however, when
enriched it can be observed easily.

36

18

07-Sep-16

Importantpointsaboutnuclei
Line-width
The line-widths of spin- nuclei are generally small and sharp (long spin lattice

relaxation, T1x) unless affected by paramagnetism or anisotropy.

Broad signals are usually an issue for quadrupolar nuclei (spin > ) and are

broader due to small long spin lattice relaxation, T1x .

In many cases, the line-width is too broad to be detected with a high-resolution
spectrometer, for example, the

127I

line-width of aqueous KI in a 400 MHz

spectrometer is of the order of 2 kHz but for the larger and less symmetric
iodobenzene it is of the order of 10 MHz, much too broad to be observed by a highresolution spectrometer and more than an order of magnitude wider than its
chemical shift range.

37

Important points about nuclei*

Chemical shift dispersion
Chemical shift dispersion varies widely between nuclei as a function of both

electronic and chemical properties with some tendency to larger dispersions for
heavier nuclei.
The chemical shift range varies from around 30 ppm for hydrogen to 20000 ppm for Pb
H 20 ppm;

B 200 ppm;

Li, 10 ppm,

Al 500 ppm;

C 650 ppm;
Si, 400 ppm,

N 1000 ppm; F, 800 ppm;

P 700 ppm;

Cl, 1000 ppm;

Na, 20 ppm
H, Li and Na does not have valence p electrons; no paramagnetic terms
When the chemical shift range is very large, the chemical shift is extremely sensitive

to environmental parameters and the signals may be broadened by temperature

gradients across the sample.
The chemical shift ranges for different isotopes of the same element are almost

identical.
38

* The Multi-nuclear approach to NMR spectroscopy, J. B. Lambert F. R. Riddell, 1983

19

07-Sep-16

NMR properties of some commonly encountered spin nuclei

Nucleus

Natural
RelativeNMR
Abundance
frequency
(%)
(MHz)(B0 =4.7T)

Magnetogyric Receptivity standard

ratio relativeto Reference
1H
(107 T1s1)
compound

1H

99.99

200.0

26.75

13C

1 11
1.11

50 2
50.2

19F

100.0

29Si

Chemical
shiftrange
(ppm)

1.0

(CH3)4Si

-30 to 20

6 73
6.73

0 016
0.016

(CH3)4Si

-100
100 to 400

188.2

25.18

0.83

CFCl3

-200 to 200

4.7

39.8

-5.32

0.0078

(CH3)4Si

-350 to 40

31P

100.0

81.0

10.84

0.066

85% aq.
H3PO4

-100 to 250

77Se
S

7 58
7.58

38 2
38.2

5 101
5.101

0 0005
0.0005

M 2Se
Me
S

-300
300 tto 200

119Sn

8.58

74.5

-10.03

0.052

Me4Sn

-1000 to
8000

195Pt

33.8

43.0

5.83

0.0099

[Pt(CN)6]2-

-200 TO
15000
39

Examples for I > 1/2

13C

NMR of CDCl3

D has I = 1
-1
1
0
D

Bo

40

20

07-Sep-16

Examples for I > 1/2

e.g. 11BH411B

-3/2
-1/2

has I = 3/2,

11B

1/2
3/2

Bo

1J
BH

The proton (1H) spectrum

spectr m is
therefore a QUARTET, with
intensities 1 : 1 : 1 : 1.
(Remember fine structure
due to the spins on the
other nuclei):

1H

resonance

The 11B resonance will be a 1 : 4 : 6 : 4 : 1 quintet i.e. a normal AX4

system, since it is the 1H nuclei, with I = 1/2, that are doing the splitting

41

Consider PF5

Fluxionality

F1
F4 P
F5
D 3h

F
F3

F4

Exchange is too rapid

To monitor in NMR

F2

F1
2
P F
3
F
C 4v
F5

F4 P
F3
D 3h

F1
F5

F4
F2

F1

F5

F3

Berry pseudorotation
from Inorganic Chemistry
Huheey and Keiter

F1
F4 P

Exchange is slow

F5
D 3h

Cl
Cl
19F

NMR of PF3Cl2 at various temperature

21

07-Sep-16

Summary:ParametersinNMR
Summary:ParametersinNMR
1. Chemicalshift(
Chemicalshift()
)
ppm
Structuralinformation
PEAK REF (Hz)
-----------------------------Freq of the nuclei(MHz)

(ppm
ppm)) =

is dimensionless (independent from the applied field)

changes with the applied field

2. Couplingconstant(J)
Couplingconstant(J) Hz
Structuraland
Conformationalinformation
3. Areaofpeaks
Relativeproportionofnuclei
4. MolecularMotion(fluxtionality
MolecularMotion(fluxtionality))

GeometryandNMRaswellasIntegration

Fax
Feq
Feq

Feq
Feq

IF5
has
a
square-pyramidal
geometry, with one axial fluorine and
four equatorial fluorines. Coupling
between the inequivalent fluorines
should give rise to a quintet for the
Fax resonance and a doublet for the
Feq resonance with intensity ratio of
1:4 respectively

Stick diagram
Fax quintet

Feq doublet

44

22

07-Sep-16

Practicequestions
1. Predict the 1H, 19F and 31P NMR (wherever applicable) spectra for the
following molecules and predict its structure
(a) PCl3F2

b) ClF3 (c) diethylphosphite [HP(OEt)2] (d) MePF2

2. Oxidative addition of methyl iodide to Pd(PPh3)4 would be expected to give

either a cis- or trans-(PPh3)2Pd(CH3)I. In the

31P{1H}

NMR, a pair of doublets

were observed at 26 and 32 ppm with a coupling of 23 Hz. The 1H NMR gave
a dd (7 Hz and 5 Hz) at 1 ppm. Which isomer of the product was formed.
(do not consider Pd-P coupling; dd: doublet of doublet)
3. Calculate the energy difference between the two spin state of a proton under
the magnetic field strength of 1.41 tesla

45

23