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
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

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

MULTIPLETS

H C

H C H

H C

H C H

two neighbors n+1 = 3 triplet

one neighbor n+1 = 2 doublet

singlet doublet triplet quartet quintet sextet septet

1,1,2-Trichloroethane
integral = 2

Cl H H C C Cl
integral = 1

Cl H

EXCEPTIONS TO THE N+1 RULE

IMPORTANT !
1)

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)

Protons in the same group usually do not split one another

H C H H
or

H 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.
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

SOME COMMON PATTERNS

SOME COMMON SPLITTING PATTERNS

X CH CH Y
(X=Y)

CH3 CH

CH2 CH

CH3 CH2

X CH2 CH2 Y
(X=Y)

CH 3 CH CH 3

SOME EXAMPLE SPECTRA WITH SPLITTING

NMR Spectrum of Bromoethane

Br CH2CH3

NMR Spectrum of 2-Nitropropane

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

NMR Spectrum of Acetaldehyde

O CH3 C H

offset = 2.0 ppm

INTENSITIES OF MULTIPLET PEAKS

PASCALS TRIANGLE

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 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 + 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

THE COUPLING CONSTANT

THE COUPLING CONSTANT

J
H H 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.

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

The shift is dependant on the field

J = 7.5 Hz

7.5 Hz

ppm

100 MHz

200 Hz 100 Hz J = 7.5 Hz J= 7.5 Hz

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

Why buy a higher field instrument?

50 MHz J = 7.5 Hz

Spectra are simplified!

3
100 MHz J = 7.5 Hz

Overlapping multiplets are separated.

Second-order effects are minimized.

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.
3J

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.

LONG RANGE COUPLINGS

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

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.

SOME REPRESENTATIVE COUPLING CONSTANTS

H H
vicinal

C C
H C C H H C C H C H
H ax He q

6 to 8 Hz

three bond

3J

trans cis geminal

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

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 (d, 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.