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Nuclear Magnetic Resonance Ii
Nuclear Magnetic Resonance Ii
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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.
The more electron density around a proton, the more the
shield, the lower magnetic field affecting the proton ,
The less electron density , the less the shield , the
higher magnetic field.
This represents the electron density of a C-H bond. How much electron
Z density is on the proton depends on what else is attached to the carbon. If Z
C H 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.
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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.
In the classical NMR experiment, magnetic field strength must be increased for a5
shielded proton to flip at the same frequency.
Low external applied field Higher external applied field
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Protons in a molecule
upfield
higher frequency
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The CHEMICAL SHIFT
The “chemical shift” is a field independent value.
chemical shift in Hz
shift
= = = ppm
spectrometer frequency in MHz
Organic protons absorb downfield (to the left) of the TMS signal.
4. Hydrogen bonding.
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1. DESHIELDING BY ELECTRONEGATIVE
ELEMENTS
-
Chlorine “deshields” the proton,
NMR CHART
most TMS
deshielded
deshielding increases with the
electronegativity of atom X
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SUBSTITUTION EFFECTS ON CHEMICAL SHIFT
most
Cumulative Effect
The effect
deshielded increases with
CHCl3 CH2Cl2 CH3Cl
greater numbers
7.27 5.30 3.05 ppm of electronegative
atoms.
most
deshielded CH2Br CH2CH2Br X CH2CH2CH2Br
3.30 1.69 1.25 ppm
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As s-character of carbon atom increases, the electronic cloud is held more closer to
the carbon and provides less electron density for shielding of protons, and thus the
chemical shift, δ, increases (shifted downfield).
According to the above reasoning, the following trend for the chemical shift is
expected:
C H > C H > C H
sp sp2 sp3
expected to be observed
at > 7
s-character increases
(down field - higher )
But in fact, we have the following order: actually observed
at = 2-3
C H > C H > C H
sp2 sp sp3
This suggested that other factors than the sp character of carbon might affect the
chemical shift in this case. The above discrepancy can be explained by what is
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called Magnetic Anisotropic Effect.
3. MAGNETIC ANISOTROPIC FIELDS
DUE TO THE PRESENCE OF -BONDS
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Aromatic protons
= 7-8 ppm
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Vinyl (Olefinic) protons,
= 5-6 ppm
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Acetylene protons
̃ ≈ 2.5 ppm
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Aldehyde proton
= 9-10 ppm
Electronegative
oxygen atom
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4. HYDROGEN BONDING
O-H and N-H Signals
HYDROGEN BONDING DESHIELDS PROTONS
The chemical shift depends
R on how much hydrogen bonding
is taking place (observed in high
O H H concentrated solutions).
Hydrogen bonding lengthens the
O H O R O-H bond and reduces the valence
electron density around the proton
R
it is deshielded and shifted
downfield in the NMR spectrum.
H3C O
O In methyl salicylate, which has strong
H
internal hydrogen bonding, the NMR
absorption for O-H is at about 14 ppm,
O
(highly downfield(
12 11 10 9 8 7 6 5 4 3 2 1 0 (ppm)
H
CH2F CH2Ar C-CH-C
RCOOH RCHO C=C CH2Cl CH2NR2
C
acid aldehyde olefinic CH2Br CH2S
C-CH2-C
sp2 CH2I C C-H
C=C-CH2 C-CH3
CH2O
CH23NO2 CH32-C- sp3 23
sp sp sp O
EQUIVALENT AND NONEQUIVALENT PROTONS
H
All of the protons in a molecule which are in chemically H H H2C CH2
identical environments will often exhibits the same
H2C CH2
chemical shift i.e., shows one signal in NMR spectrum at
H H C
the same value of . H2
H
O
The protons in this case are said to be (CH3)4Si
H3C CH3
chemically equivalent
Molecules giving rise to one NMR absorption signal
CH3 All protons are chemically equivalent
O
H H
H2C C O CH3
H2C C O CH3
H H
O On the other hand, molecules which have sets
CH3
of protons which are chemically distinct (have
O H different chemical environments) from one
CH3 H3C O C Cl another give rise to different absorption
H3C O
H signals from each other.
Molecules giving rise to two NMR absorption signals
Two dif f erent sets of chemically equivalent protons
• The NMR spectrometer has the capability to electronically integrate the area under each
peak.
NMR spectrum can reveal the number of protons assigned for each signal
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SPIN-SPIN SPLITTING
Chapter 13 30
THE ORIGIN OF
SPIN-SPIN SPLITTING
HOW IT HAPPENS
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Doublet
1 adjacent proton
Chapter 13 32
Triplet
2 Adjacent Protons
Chapter 13 33
n + 1 RULE
MULTIPLETS
this hydrogen’s peak these hydrogens are
is split by its two neighbors split by their single
neighbor
singlet
doublet
H H H H triplet
quartet
C C C C quintet
H H sixtet
two neighbors
septet
n+1 = 3 one neighbor
triplet n+1 = 2
doublet
Where n is the number of EQUIVALENT protons on
Adjacent carbon atoms 34
EXCEPTIONS TO THE n+1 RULE
IMPORTANT !
1) Protons that are equivalent by symmetry usually do not split one another
X CH CH Y X CH2 CH2 Y
no splitting if x = y splitting if x y
two triplets
2) Protons in the same group usually do not split one another
H H
C H or C
H H
3) Splitting is not observed if the protons are separated by more than three
bonds
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INTENSITIES OF MULTIPLET PEAKS
PASCAL’S TRIANGLE
Intensities of
multiplet peaks 1 singlet
1 1 doublet
1 2 1 triplet
1 3 3 1 quartet
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NMR spectrum indicates the carbon skeleton
Spin-spin splitting gives the number of equivalent protons on
adjacent carbon atoms
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Summary
INFORMATION WE CAN GET FROM NMR SPECTRUM
Number of 1H-NMR signals = Number of kinds of protons.
NMR spectrum can reveal the number of protons assigned for each
signal (integral lines : no. of protons in each signal).
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Typical Values
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