CHEMICAL SHIFT

PACKARD 1951

CH3- CH2-OH
3 Different values for the ω of
protons
∴ 3 Different chemical
environments?
 Reference
ω in absolute unit is difficult
∴ Difference in frequency w. r. to some
references is measured. e.g.
1H, 13C Si(CH3)4
19F CFCl3
31P H3PO4
17O H20
15N NH3, CH3NO2
 WHY TMS ?
Inert, low boiling, soluble in common
solvents, sharp signal

Chemical shift ?
A function of nucleus and its environment

molecular quantity measured from a

reference
δ is
Proportionality constant

Dimensionless

Increases in downfield direction with increasing frequency

δTMS = 0

60 MHz: 1ppm = 60 Hz
 NUCLEAR SHIELDING

S- orbital diamagnetic p, d, f – orbitals no

upfield shift spherical symmetry
paramagnetic downfield
Bn < Bo shift
Bn = Bo - ΔB Bn > Bo
Bn = Bo + ΔB
Where
Bo applied field
Bn field experienced by
nucleus
ΔB nuclear shielding
Range of chemical shift (maximum)
1H 30 ppm
13C 400 ppm
19F 1000 ppm
 POLAR EFFECTS
CH4 CH3I CH3Br CH3Cl CH3F

δ 0.8 2.16 2.68 3.05 4.26

EN 2.1 2.5 2.8 3.0 4.0

δ 7.27 5.42 9.17

(0) (-1.7) (+1.9)
charge /c 1/5 or 0.2e/C 1/7 or 0.143 + ve
 HYDROGEN BONDING

7.45 - 4.37

12.0

12.1
Acetylenic Protons, 1.5-3.5
Vinyl Protons, 4-8
Aromatic Protons, 6-9
Aldehyde Proton, 9-10

Electronegative
oxygen atom
ANISOTROPIC EFFECT
ANISOTROPIC EFFECT
δ
δ

δ
δ
Pascal Triangle
S = 2nI + 1
Vicinal Coupling
Vicinal Coupling
Geminal Coupling
Geminal Coupling -E

+E

+E

-E
AX A X
A' A'' X' X''

A' = A + 2E A'' = A - 2E

A'' - A' = -4E

J = - ve
X' = X+ 2E X'' = X - 2E

X'' - X' = -4E

Geminal Coupling
Vicinal Coupling: Dihedral Angle Dependence
Vicinal Coupling: Dihedral Angle
Dependence 60o

Ha Ha
C He
He 180o 60o
He
C He
Ha
Ha

 J range
aa 180o 8-14 8-12

ee 60o 1-7 2-3

ae 60o 1-7 2-3
H

H
H H
Jcis = 7-10 Hz Jtrans = 12-18 Hz
Long Range Coupling
W Coupling
 AB Quartet

600 MHz

300 MHz

100 MHz

60 MHz
AMX
ABC
 Chemical and Magnetic Nonequivalence
Chemically non-equivalent = different chemical shifts
 Chemical and Magnetic Nonequivalence
Magnetically non-equivalent = different coupling constants
 References

R. J. Abraham, J. Fisher, P. Loftus, Introduction to NMR Spectroscopy, John

Wiley and Sons, 1988, 286 pp
THANK YOU
irishi@iitb.ac.in
 I = 1
n = 0

n = 1 CDCl3
1 1 1
n = 2 CD2Cl2
1 2 3 2 1
n = 3 CD3COCD3
1 3 6 7 6 3 1
Compound Jgem No. of adjecent
 bonds
CH4 -12.4 0

CH3
-14.5 1

CH3-C N -16.9 2

CN
-20.4 4
CN
 Dependence of Jvic on the
electronegativity of substituent

Ha Ha
C He
X
He Jae = 5.5 Hz
C X
Ha
Ha

X X
C He
He Jae = 2.5 Hz
He
C He
Ha
Ha
 Ha Cl
Cl Hb
Cl Hb'

Jab = 7.9 - 0.7 E

Where E = Ex- EH Jab = 7.9- (0.7 x 3 x 0.95)
= 5.9 Hz
= 3.15-2.20

= 0.95

EN substituents reduce J
 Dependence 3J on bond angles

Hb H
'
10-13 5.1-7.0
Ha H

H H
9-12.6 2.5-3.7
H H

H H
8.8-11 0.5-1.5
H H

Ha-C-C = Hb-C-C = '

= '
& ' increase with decreasing
ring size, J decrease
 P1
H HA
C P2 HA
H C
HB
HB

CH2 protons lie in P1 orbitals Both CH2 protons lie on the

same side of orbital
 orbitals lie in P1 orbitals
P1 & P2 are parallel
20o 74o
O O
H H
H O H O
H H H H

J = -16 to -17 J = -12 to -13

AB2, AB3, ABX

12 lines
AB2
ABC
AA' XX' 300 MHz
AA' XX' 300 MHz
AA' BB' 100 MHz
3. Shift Reagents
5 4
6 3
7 N 2
8

4, 8

2 3, 5, 7

+ 0.3 mmol Eu (DPM)3

2 8 4 3 5 7
 R1
O
M
O
R2 3

7 2
M= 63Eu = [Xe] 4f 6s Downfield shift
3 2
59Pr = [Xe] 4f 6s Upfield shift

Sample should be a Lewis base

ROH, RNR21, RCOR1, RCHO, ROR1,
1
RCO2R , RCN etc...
 RCH2X + EuL3

X NH2 OH COR CHO OCH2R CO2Me CN

 35 25 15 11 10 7 5

Contact shift
Pseudocontact shift

Limitations
Paramagnetic line broadening due to
short relaxation time for the unpaired
electrons
R1 R2 L ML3

CMe3 CMe3 DiPivaloylMethane M(DPM)3

CMe3 C3F7 HeptaFluoroDimethyl M(FOD)3

octanedione

C2F5 C2F5 DecaFluoroHeptaneDione M(FHD)3

 Chiral Shift Reagents (CSRs)
For determination of enantiomer composition

O Eu(t-cam)3
O M/3 tris(3-tert-butylhydroxy-methylene-d-
camphorato)-europium (III)

F F
F Eu(tacam)3
O tris(3-trisfluoroacetyl-d-
O M/3 camphorato)europium
 C3F7 Eu(hfbc)3
tris(3-heptafluorobutyryl-d-
O camphorato)europium (III)
O M/3

Eu(dcm)3
tris(d,d-dicamphoryl-methanato)
O europium (III)
O M/3

CSR substrate ratio 0.5-1

Observed chemical shift difference 0.1-0.5

ocassionally upto 4 ppm
 13
C - H coupling

100 MHz
1
H NMR

CHCl3
13 13
CHCl3 200 Hz CHCl3

SSB SSB

SSB - Spinning side band, varies

when spinning rate is varied

1
H NMR 200 Hz = 2 ppm
13
C NMR 200 Hz = 8 ppm
 1
J C-H = 500 where  = extent of S character

1
JC-H (Hz)
Hybridisation  Calc. Eg. Obsvd.

sp3 0.25 125 CH4 125

H H
sp2 0.33 167 156
H H

sp 0.50 250 H H 248

13
1JC-H = 162 Hz C-13C low probability