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Magnetic Shielding
Chemical Shift
MAGNETIC SHIELDING
The electrons in a bond shield the nuclei from the magnetic field.
A moving charge (electron) creates a magnetic field, and the field
created by the moving electrons opposes the applied magnetic
field Bo.
The electrons in a bond shield the nuclei from the magnetic field.
Z
C
This represents the electron density of a C-H bond. How much electron
density is on the proton depends on what else is attached to the carbon. If Z
is an elelctronegative atom, the carbon becomes electron deficient and pulls
some of the electron density away from the H. if Z is an electron donating
group, more electron density ends up on the H.
Shielded Protons
The effective magnetic field, therefore, what the hydrogen
nuclei actually sense through the surrounding electronic
environment is always less than the actual applied magnetic
field B0.
Beffective = Bapplied Blocal
Protons in a molecule
upfield
Lower frequency
downfield
higher frequency
parts per
million
chemical
shift
shift in Hz
=
spectrometer frequency in MHz
= ppm
Tetramethylsilane (TMS)
CH3
H3C
Si CH3
CH3
1. DESHIELDING BY ELECTRONEGATIVE
ELEMENTS
Cl
electronegative
element
NMR CHART
deshielded
protons appear
at downfield
(higher )
highly shielded
protons appear
at upfield
(lower )
11
ELECTRONEGATIVITY DEPENDENCE OF
CHEMICAL SHIFT
most
deshielded
CH3F
CH3OH
CH3Cl
CH3Br
CH3I
CH4
(CH3)4Si
Cl
Br
Si
4.0
3.5
3.1
2.8
2.5
2.1
1.8
4.26
3.40
3.05
2.68
2.16
0.23
TMS
deshielding increases with the
electronegativity of atom X
12
most
deshielded
most
deshielded
Cumulative Effect
CH2Br
3.30
CH2CH2Br
1.69
The effect
increases with
greater numbers
ppmof electronegative
atoms.
CH2CH2CH2Br
1.25
13
pp
2. s-CHARACTER
(HYBRIDIZTION OF CARBON ATOM)
14
expected to be observed
at > 7
(down field - higher )
actually observed
at = 2-3
15
Aromatic protons
= 7-8 ppm
17
18
Acetylene protons
2.5 ppm
19
Aldehyde proton
= 9-10 ppm
Electronegative
oxygen atom
20
4. HYDROGEN BONDING
O-H and N-H Signals
HYDROGEN BONDING DESHIELDS PROTONS
R
O
H
O
R
H
H
O R
+
-I
H3C O
H
O
22
-OH -NH
aromatic
DESHIELDED
DOWNFIELD
HIGHFREQUENCY
LARGE
SHIELDED
UPFIELD
LOWFREQUENCY
SMALL
0 - 5
CHCl3 , H
3 - 5
7-8
10-12
1.5 - 3
4.5 - 7
9-10
12
11
10
PROTON IN
ELECTRON-RICH
ENVIRONMENTS
H
RCOOH
RCHO
C=C
acid
aldehyde
olefinic
sp2
TMS
0 2
4
CH2Ar
CH2F
C-CH-C
CH2NR2
CH2Cl
C
CH2S
CH2Br
C-CH2-C
C C-H
CH2I
C=C-CH2 C-CH3
CH2O
sp3
CH23NO2 CH23-Csp
sp sp O
(ppm)
23
24
INTEGRATION OF A PEAK
Not only does each different type of hydrogen give a
distinct peak in the NMR spectrum, but we can also tell
the relative numbers of each type of hydrogen by a
process called integration.
In the NMR spectrum, the area under each peak is proportional to the
number of hydrogens generating that peak.
The NMR spectrometer has the capability to electronically integrate
the area under each peak.
2,2-dimethyl-1-propanol (C4H12O)
26
Modern spectrometers
automatically print out the
integrals as numbers on
the spectrum
NMR spectrum can reveal the number of protons assigned for each
signal
27
SPIN-SPIN SPLITTING
28
SPIN-SPIN SPLITTING
Often a group of hydrogens will appear as a multiplet
rather than as a single peak.
Multiplets are named as follows:
Singlet (s)
Doublet (d)
Triplet (t)
Quartet (q)
Quintet (quin)
Sixtet (six)
Septet (sept)
Multiplet (m)
1,1,2-Tribromoethane
Nonequivalent protons on adjacent carbons.
Chapter 13
30
THE ORIGIN OF
SPIN-SPIN SPLITTING
HOW IT HAPPENS
Spin-spin splitting arises because hydrogen on
adjacent carbon atoms can sense one
another
31
Doublet
1 adjacent proton
Chapter 13
32
Triplet
2 Adjacent Protons
Chapter 13
33
n+1
RULE peak
this hydrogens
is split by its two neighbors
H
two neighbors
n+1 = 3
triplet
MULTIPLETS
singlet
doublet
triplet
quartet
quintet
sixtet
septet
one neighbor
n+1 = 2
doublet
34
no splitting if x = y
2)
H
C H
H
H
or
C
H
35
1
1 1
1 2
1
1 3 3 1
singlet
doublet
triplet
quartet
36
37
Summar
y
INFORMATION WE CAN GET FROM NMR SPECTRUM
Number of 1H-NMR signals = Number of kinds of
protons.
Typical Values
39
40