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Professor S. SANKARARAMAN
Department of Chemistry
Indian Institute of Technology Madras
Chennai 600 036
sanka@iitm.ac.in
HISTORICAL PERSPECTIVE
Discovery of NMR phenomenon in 1945
Purcell, Torrey and Pound Harvard University USA
Bloch, Hansen and Packard Stanford University USA
When ethanol was placed between pole pieces of an
electromagnet and irradiated with electromagnetic
radiation it absorbed radiation in the radio frequency
region. When the magnetic field was turned off no
absorption was observed.
Purcell and Bloch Nobel prize in Physics 1952
For the discovery of NMR.
Atomic mass
Even
Even
Odd
Atomic number
Even
Odd
Even or Odd
Spin
zero
multiple of 1
multiple of
Examples:
I=0
I = integer
I = half integer
12C , 16O
6
8
14N (1), 10B (3), 2H (1)
7
5
1
1H (1/2), 13C (1/2), 15N
1
6
7
17O (5/2) 33S (3/2)
8
16
(1/2)
Spin
g
(rad T-1 s-1)
1H
Natural
abundance (%)
26.7
99.9
4.107
0.015
13C
6
6.72
1.10
19F
9
25.18
100
31P
10.84
100
-5.32
4.67
2H
15
29Si
14
+ 1/2 b
E = hn = (h/2p)Bog
E = hn
no field
Bo
increasing filed strength Bo
n = (Bog)/2p
- 1/2 a
n (MHz)
DE (J)
Na / Nb
T oC
2.35
100
6.7 x 10-26
17 ppm
17
4.70
200
22.5 x 10-26
57 ppm
17
7.0
300
33.5 x 10-26
85 ppm
17
2.35
100
6.7 x 10-26
28
13
-100
+100
n = (Bo g)/ 2p
Nucleus is surrounded by electrons
Electrons have charge as well as spin
The magnetic field due to the spinning electron
shields the nucleus from the external magnetic
field. This is diamagnetic shielding.
The nucleus does not feel Bo, but Beff = Bo(1-s)
Beff is the effective magnetic field felt by nucleus
s is the shielding constant
d=
(in ppm)
0
0
60 MHz spectrometer
10 ppm
4000 Hz
0
400 MHz spectrometer
MeI
MeBr
MeCl
MeF
2.2
2.6
3.1
4.3
MeCl
CH2Cl2
CHCl3
3.1
5.3
7.2
MeOH
MeF
MeNO2
3.4
4.3
4.3
2. Anisotropic effects:
Spherical electron density induced magnetic field
will be uniform in space isotropic effect
For example s electron spherical
H d 1.80
+
d 5.28
+
H
deshielding
- deshielding
+
shielding
shielding
Bo
Bo
shielding
+
Bo
Bo
d 7.28
H
deshielding
d 9.5
+
shielding
Bo
deshielding
1.03
H
H -0.51
1.27
Me
0.70
Me
H
8.14-8.67
H
H
7.29
H
1.44
-4.2
H
H
H
H
2.82
H
H 9.3
-3.0
4.23
H
NO2
NO2
H
4.43
3.37
H
OH
OH
H
3.93
CH3 CH2 - OH
OCH2Ph
O
PhCH2O
PhCH2O
PhCH2O
SPh
a
Absence of any interacting protons
d
No neighboring protons
No spin-spin coupling only a single peak for each
chemically different proton
Case 2
spin-spin interaction
bb
da
ba
db
Case 2
ab
Jab
Jab
da
db
aa
Ha Hb
only two transitions
one for Ha and one
for Hb
four transitions,
two each for Ha and
Hb
http://www.cem.msu.edu/~reusch/VirtualText/Spectrpy/nmr/nmr1.htm
http://www.cem.msu.edu/~reusch/VirtualText/Spectrpy/nmr/nmr1.htm
http://www.cem.msu.edu/~reusch/VirtualText/Spectrpy/nmr/nmr2.htm#pulse
Ha
C C
Hb
Ha
C C Hb
Hb
Ha
C C
Ha Hb
CH3 - CH2
CH3-CH2-CH2
CH3-CH-CH3
1
11
121
1331
14641
1 5 10 10 5 1
http://www.cem.msu.edu/~reusch/VirtualText/Spectrpy/nmr/nmr1.htm
CH3CH2Br
CH3COOCH2C6H5
HCOOCH2CH3
A
C4H8O
CH3COCH2CH3
B
C4H8O2
CH3COOCH2CH3
C5H7NO2
CH3CH2O
CH2C N
C4H7O2Br
CH3-CH2-CH(Br)-COOH
H3C
CH3
CH2CH3
CH3
H3C
CH3
CH3
H
CH3
OH O
H
Ha
O
CH3
Hb
CH3
H
H3C
H
H
O
O
CH3
CH3
H3C
CH3
O
H
H
CH3CH2 O
O
O
O CH2CH3
O
O
O
O
CH2CH3
CH2CH3
H3C
C10H12O3
H
O
CH3
3H
3H
5H
1H
CH2CH2OH
2H
5H
2H
1H
C9H11Br
CH2CH2CH2Br
5H
2H
2H
2H
NH2
C6H5NBr2
Br
Br
H
H
2H
1H
2H
Ha
Y
X
Z
R
Hb
Ha
Hb
Ha
Hx
Hm
X
Ha
Ha'
Hb
Hb'
Y
Ha'
Ha
X
Hb
Y
Hb'
C6H8N2
H3C
2H
1H
1H
1H
NH2
3H
Dimethyl cyclopropanedicarboxylate
Conformational changes
Restricted rotation around C-C and C-X bonds
Aggregation phenomena
Fluxional properties of molecules
Temperature range typically -150 oC to +150 oC
provided solubility and solvent mp/bp permit
Processes with activation barrier typically in the range
of 8-25 Kcal/mole can be studied
N
Me
O
O
Me
N
Me
Me
N
Me
Conformational changes
Interconversion of chair
form of cyclohexane
H
H
Cyclohexane-d11
D2
D2
H
NH
D2
D2
NH
Fluxional behaviour of
large annulenes
H
H
H
H
H
H
H
H
H
H
H
H
[18]annulene
H
H
H
H
H
H
H
H
Me
2
Al
Me
Me
Me
Me
Al
Me
Me
Al
Me
Me
13C-NMR
spectroscopy
FT-NMR technique
Two types of NMR spectrometers
Continuous wave (CW)
Fourier Transform (FT)
Signal
intenisty
Relaxation agents:
Paramagnetic relaxation agents such as Cr(acac)3 reduces
the longitudinal relaxation
This allows faster signal averaging
CH3CH2 O
O
2
1
O CH2CH3
4
2,3
4
1
O
O
1 O
4
3
CH2CH3
CH2CH3
5
3
CDCl3
2
1
H3C
NH2
O
CH3CH2O
CH2C N
HO
OH
N3
O
O
O
AcO
OAc
N3
AcO
OAc
H
N
O
O
O
A
O
B
N
N
N
N
Het-2D-J resolved
2-chlorobutane
a-Pinene
References:
J. B. Lambert, H. F. Shurvell, L. Verbit, R. G. Cooks, G. H. Stout
Organic Structural Analysis
Macmillan, New York, 1976
W. Kemp
Organic Spectroscopy, 3rd Edition, Macmillan, New York, 1991
D. H. Williams, I. Fleming
Spectroscopic Methods in Organic Chemistry, 4th Edition
Tata McGraw Hill, New Delhi, 1988
R. M. Silverstein, G. C. Bassler, T. C. Morrill
Spectroscopic Identification of Organic Compounds, 5th Edition
John Wiley, New York, 1991
H. Gnther
NMR Spectroscopy, 2nd Edition
John Wiley, New York, 1994