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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 Doublet Triplet Quartet Quintet Septet Octet Nonet
This happens because of interaction with neighboring hydrogens and is called SPIN-SPIN SPLITTING
1,1,2-Trichloroethane
Cl H H C C Cl Cl H
Two types of H
1,1,2-Trichloroethane
The two kinds of hydrogens do not appear as single peaks, rather there is a triplet and a doublet.
integral = 2
Cl H H C C Cl
integral = 1
Cl H
triplet
doublet
The subpeaks are due to spin-spin splitting and are predicted by the n+1 rule.
n+1
RULE
1,1,2-Trichloroethane
integral = 2
Cl H H C C Cl
integral = 1
Cl H
MULTIPLETS
H C
H C H
H C
H C H
1,1,2-Trichloroethane
integral = 2
Cl H H C C Cl
integral = 1
Cl H
Protons that are equivalent by symmetry usually do not split one another
X CH CH Y
no splitting if X = Y
X CH2 CH2 Y
no splitting if X = Y
2)
H C H
The n+1 rule applies principally to protons in aliphatic (saturated) chains or on saturated rings.
CH3 CH2CH2CH2CH2CH3
or
YES
YES
but does not apply (in the simple way shown here) to protons on double bonds or on benzene rings.
H H CH3 H CH3
NO
NO
CH3 CH
CH2 CH
CH3 CH2
X CH2 CH2 Y
(X=Y)
CH 3 CH CH 3
Br CH2CH3
H CH3 C CH3 + N O O-
1:6:15:20:16:6:1
in higher multiplets; the outer peaks are often nearly lost in the baseline
PASCALS TRIANGLE
Intensities of multiplet peaks
1 The interior 1 1 entries are the sums of 1 2 1 the two numbers immediately 1 3 3 1 above. 1 4 6 4 1 1 5 10 10 5 1 1 6 15 20 15 6 1 1 7 21 35 35 21 7 1
singlet
doublet
triplet quartet quintet sextet septet octet
THE CHEMICAL SHIFT OF PROTON, HA, IS AFFECTED BY THE SPIN OF ITS NEIGHBORS
aligned with Bo + 50 % of molecules opposed to Bo - 50 % of molecules
H C
HA C
H C
HA C
Bo
downfield neighbor aligned upfield neighbor opposed
At any given time, about half of the molecules in solution will have spin + and the other half will have spin -.
SPIN ARRANGEMENTS
one neighbor n+1 = 2 doublet one neighbor n+1 = 2 doublet
H
C
H
C
H
C
H
C
yellow spins
blue spins The resonance positions (splitting) of a given hydrogen is affected by the possible spins of its neighbor.
SPIN ARRANGEMENTS
two neighbors n+1 = 3 triplet one neighbor n+1 = 2 doublet
H C
H C H
H C
H C H
methine spins
methylene spins
SPIN ARRANGEMENTS
three neighbors n+1 = 4 quartet two neighbors n+1 = 3 triplet
H H
C
H
C
H
C
H
C
H
methyl spins
methylene spins
H H
J
The coupling constant is the distance J (measured in Hz) between the peaks in a multiplet. J is a measure of the amount of interaction between the two sets of hydrogens creating the multiplet.
100 MHz
FIELD COMPARISON
200 Hz 100 Hz
Coupling constants are constant - they do not change at different field strengths
J = 7.5 Hz
7.5 Hz
6 200 MHz
5
Separation is larger
3
400 Hz
200 Hz
J = 7.5 Hz
7.5 Hz
ppm
100 MHz
6 200 MHz
3
Separation is larger
1
400 Hz 200 Hz
Note the compression of multiplets in the 200 MHz spectrum when it is plotted on the same scale as the 100 MHz spectrum instead of on a chart which is twice as wide.
J = 7.5 Hz
ppm
50 MHz J = 7.5 Hz
3
100 MHz J = 7.5 Hz
H H C C
This is sometimes called vicinal coupling. It is designated 3J since three bonds intervene between the two hydrogens.
Another type of coupling that can also occur in special cases is 2J or geminal coupling H ( most often 2J = 0 ) C H Geminal coupling does not occur when 2J the two hydrogens are equivalent due to rotations around the other two bonds.
C
4J
, for instance, occurs mainly when the hydrogens are forced to adopt this W conformation (as in bicyclic compounds). Couplings larger than 3J (e.g., 4J, 5J, etc) are usually called long-range coupling.
C C
H C C H H C C H C H
H ax He q
6 to 8 Hz
three bond
3J
11 to 18 Hz
H
three bond
three bond two bond
3J
6 to 15 Hz 0 to 5 Hz
3J 2J
Hax,Hax = 8 to 14
Hax,Heq = 0 to 7 Heq,Heq = 0 to 5 three bond
3J
H eq
H ax
cis
H
C C H
6 to 12 Hz
4 to 8 Hz
trans
H
three bond
3J
4 to 10 Hz
three bond
3J
H C C C H
H C C C H
0 to 3 Hz
four bond
4J
0 to 3 Hz
four bond
4J
Couplings that occur at distances greater than three bonds are called long-range couplings they are usually small (<3 Hz) and frequently nonexistent (0 Hz).
OVERVIEW
3) NMR spectrum
a chemist can often figure out the complete structure of an unknown molecule.
Reveals the enviroment of each hydrogen and the relative numbers of each type.