SPIN-SPIN SPLITTING

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
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

triplet

Cl H

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

Where do these multiplets come from ?

.. interaction with neighbors

this hydrogens peak

is split by its two neighbors

these hydrogens are

split by their single
neighbor

H
two neighbors
n+1 = 3
triplet

H
one neighbor
n+1 = 2
doublet

MULTIPLETS

singlet
doublet
triplet
quartet
quintet
sextet
septet

EXCEPTIONS TO THE N+1 RULE

IMPORTANT !
1)

Protons that are equivalent by symmetry

usually do not split one another
X CH2 CH2 Y

X CH CH Y
no splitting if x=y
2)

no splitting if x=y

Protons in the same group

usually do not split one another
H
C H
H

H
or

C
H

more
detail
later

EXCEPTIONS TO THE N+1 RULE

3)

The n+1 rule applies principally to protons in

aliphatic (saturated) chains or on saturated rings.
CH2CH2CH2CH2CH3

CH3
or

YES

YES

but does not apply (in the simple way shown here)
to protons on double bonds or on benzene rings.
H

CH3

CH3

NO

NO

SOME COMMON PATTERNS

SOME COMMON SPLITTING PATTERNS

X CH CH Y

CH3 CH

(x=y)

CH2 CH

X CH2 CH2 Y
(x=y)

CH3 CH2

CH3
CH
CH3

SOME EXAMPLE SPECTRA

WITH SPLITTING

NMR Spectrum of Bromoethane

Br CH2CH3

NMR Spectrum of 2-Nitropropane

H
CH3

CH3

+
N
O
O-

1:6:15:20:16:6:1

in higher multiplets the outer peaks

are often nearly lost in the baseline

NMR Spectrum of Acetaldehyde

O
CH3 C

offset = 2.0 ppm

INTENSITIES OF
MULTIPLET PEAKS
PASCALS TRIANGLE

PASCALS TRIANGLE
Intensities of
multiplet peaks

1
The interior
doublet
1
1
entries are
the sums of
triplet
1
2
the two
numbers
quartet
immediately
1
3
3
1
1
above.
quintet
1 4 6 4 1
1 5 10 10 5 1 sextet
septet
1 6 15 20 15 6 1
octet
1 7 21 35 35 21 7 1
singlet

THE ORIGIN OF
SPIN-SPIN SPLITTING
HOW IT HAPPENS

THE CHEMICAL SHIFT OF PROTON HA IS

AFFECTED BY THE SPIN OF ITS NEIGHBORS
aligned with Bo
+1/2
50 % of
molecules

opposed to Bo
-1/2

HA

HA

50 % of
molecules

Bo
downfield
neighbor aligned

upfield
neighbor opposed

At any given time about half of the molecules in solution will

have spin +1/2 and the other half will have spin -1/2.

SPIN ARRANGEMENTS
one neighbor
n+1 = 2
doublet

one neighbor
n+1 = 2
doublet

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
methylene spins

H
methine spins

SPIN ARRANGEMENTS
three neighbors
n+1 = 4
quartet

methyl spins

two neighbors
n+1 = 3
triplet

methylene spins

THE COUPLING CONSTANT

THE COUPLING CONSTANT

H H

J
J

C C H

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.

FIELD COMPARISON

100 MHz

100 Hz

Coupling constants are

constant - they do not
change at different
field strengths

400 Hz

Separation
is larger

7.5 Hz

J = 7.5 Hz

200 MHz

The shift is
dependant
on the field

200 Hz

200 Hz
7.5 Hz

J = 7.5 Hz

ppm

100 MHz

200 Hz
100 Hz
J=
7.5 Hz

J = 7.5 Hz

200 MHz
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.

Separation
is larger

1
400 Hz
200 Hz

J = 7.5 Hz

ppm

Why buy a higher

field instrument?

Spectra are
simplified!

Overlapping
multiplets are
separated.
Second-order
effects are
minimized.

50 MHz
J = 7.5 Hz

100 MHz
J = 7.5 Hz

3
200 MHz
J = 7.5 Hz

NOTATION FOR COUPLING CONSTANTS

The most commonly encountered type of coupling is
between hydrogens on adjacent carbon atoms.
3

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
2
J or geminal coupling
H
( most often 2J = 0 )
C H
Geminal coupling does not occur when
2
J
the two hydrogens are equivalent due to
rotations around the other two bonds.

LONG RANGE COUPLINGS

Couplings larger than 2J or 3J also exist, but operate
only in special situations.
H

J , for instance, occurs mainly

when the hydrogens are forced
to adopt this W conformation
(as in bicyclic compounds).
4

Couplings larger than 3J (e.g., 4J, 5J, etc) are usually

called long-range coupling.

SOME REPRESENTATIVE COUPLING CONSTANTS

H H
vicinal

6 to 8 Hz

C C

three bond

11 to 18 Hz three bond

6 to 15 Hz three bond

H
C C

trans

H
H

cis

H
C C

geminal

H
Hax

two bond

Hax,Hax = 8 to 14
Heq

Heq

0 to 5 Hz

Hax

Hax,Heq = 0 to 7 three bond

Heq,Heq = 0 to 5

cis

6 to 12 Hz

trans

4 to 8 Hz

three bond

4 to 10 Hz three bond

H
C
C H

H
C C

0 to 3 Hz

four bond

0 to 3 Hz

four bond

C H
H C C C
H

Couplings that occur at distances greater than three bonds are

called long-range couplings and they are usually small (<3 Hz)
and frequently nonexistent (0 Hz).

OVERVIEW

TYPES OF INFORMATION
FROM THE NMR SPECTRUM
1. Each different type of hydrogen gives a peak
or group of peaks (multiplet).
2. The chemical shift (in ppm) gives a clue as
to the type of hydrogen generating the peak
(alkane, alkene, benzene, aldehyde, etc.)
3. The integral gives the relative numbers of each
type of hydrogen.
4. Spin-spin splitting gives the number of hydrogens
on adjacent carbons.
5. The coupling constant J also gives information
about the arrangement of the atoms involved.

SPECTROSCOPY IS A POWERFUL TOOL

Generally, with only three pieces of data
1) empirical formula (or % composition)
2) infrared spectrum
3) NMR spectrum
a chemist can often figure out the complete
structure of an unknown molecule.

EACH TECHNIQUE YIELDS VALUABLE DATA

FORMULA

Gives the relative numbers of C and H

and other atoms
INFRARED SPECTRUM

Reveals the types of bonds that are present.

NMR SPECTRUM

Reveals the enviroment of each hydrogen

and the relative numbers of each type.