Coupling Constants (J)

Coupling constants are a very important and useful feature of an NMR

spectrum
Importantly, coupling constants identifies pairs of nuclei that are chemically
bonded to each other
1

Multiplicity identifies the number of protons (or other nuclei) that are chemical
bonded to the other nuclei

The magnitude of the coupling constants identifies the coupling partner, and
provides information on dihedral angles, hydrogen bonds, the number of
intervening bonds, and the type of coupled nuclei (1H, 13C, 15N, 19F, etc.)

Coupling Constants (J)

- spin-spin coupling, scalar coupling or J-coupling
Random tumbling of molecules averages
through-space effect of nuclear magnets
to zero
Bo

Bo

random tumbling leads to no interaction

between the spin-states despite the small

Coupling Constants (J)

- spin-spin coupling, scalar coupling or J-coupling
Instead, nuclear spin state is communicated through bonding electrons

Energy of electron spin states are

degenerate in absence of nuclear spin

With a nuclear spin, the electron spin

opposite to nuclear spin is lower energy

Number of possible energy states of nuclearelectron spin pairs increases with the
number of nuclear spins

Spin state is sensed through bonds resulting in higher or lower

energy
- aligned or anti-aligned with magnetic field

Coupling Constants
Energy level of a nuclei are affected by covalently-bonded neighbors spin-states
Mixing of Spin
Systems One and
Two

Spin System One

Spin System Two

Coupling Constants
Mixing of energy levels results in additional transitions peaks are split

+J/4

I
-J/4

J (Hz)

J (Hz)

S
+J/4

Spin-States of covalently-bonded nuclei want to be aligned

The magnitude of the separation is called coupling constant (J) and has units of Hz

Coupling Constants

Through-bond interaction that results in the splitting of a single peak into

multiple peaks of various intensities

Spacing in hertz (hz) between the peaks is a constant

Independent of magnetic field strength

Multiple coupling interactions may exist

Increase complexity of splitting pattern

Coupling can range from one-bond to five-bond

One, two and three bond coupling are most common

Longer range coupling usually occur through aromatic systems

Coupling can be between heteronuclear and homonuclear spin pairs

Both nuclei need to be NMR active i.e. 12C does not cause splitting

1
1

13

three-bond

four-bond

one-bond

1
1

five-bond

Coupling Constants

Splitting pattern depends on the number of equivalent atoms bonded to the

nuclei

Determines the number of possible spin-pair combinations and energy levels

Each peak intensity in the splitting pattern is determined by the number of spin
pairs of equivalent energy

Coupling Constants

Splitting pattern follows Pascals triangle

Number of peaks and relative peak intensity determined by the number of

attached nuclei

Peak separation determined by coupling constant (J)

Negative coupling reverse relative energy levels

1
1 1
1 2 1
1 3 3 1
1 4 6 41
1 5 10 10 5 1
1 6 15 20 15 6 1
1 7 21 35 35 21 7 1
Pascals triangle

3 attached nuclei
1

Quartet

Relative
Intensity

Coupling Constants
Common NMR Splitting Patterns

singlet doublet
1:1

triplet quartet
1:2:1 1:3:3:1

pentet
1:4:6:4:1

Coupling Rules:
1.
2.
3.
4.
5.
6.
7.

equivalent nuclei do not interact

coupling constants decreases with separation ( typically 3 bonds)
multiplicity given by number of attached equivalent protons (n+1)
multiple spin systems multiplicity (na+1)(nb+1)
Relative peak heights/area follows Pascals triangle
Coupling constant are independent of applied field strength
Coupling constants can be negative

IMPORTANT: Coupling constant pattern allow for the identification of bonded

Coupling Constants

Common NMR Splitting Patterns

Coupling Constants

Coupling only occurs between non-equivalent nuclei

Chemical shift equivalence

Magnetic equivalence

For no coupling to occur, nuclei has to be BOTH chemical shift and magnetic
equivalent

The CH3 protons (H1, H2, H3) are in identical

environments, are equivalent, and are
not coupled to one another

The Ha and Hb protons are in different

environments (proximity to Cl), are
not equivalent, and are coupled

Coupling Constants
Rules for Chemical Shift Equivalence:

Nuclei are interchangeable by symmetry operation

i.

Rotation about symmetric axis (Cn)

ii.

Inversion at a center of symmetry (i)

iii. reflection at a plane of symmetry ()

iv. Higher orders of rotation about an axis followed by reflection in a
plane normal to this axis (Sn)
v.

Symmetry element (axis, center or plane) must be symmetry

element for entire molecule

Examples of Chemical Shift Equivalent Nuclei

Ha
Hb

Ha
Ha

C
Ha

Ha

Ha
C

Hb Ha

Ha

180o
Ha
Ha

Ha
Ha

Symmetry planes

Coupling Constants
Rules for Chemical Shift Equivalence:

Nuclei are interchangeable by a rapid process

i.
ii.

> once in about 10-3 seconds

Rotation about a bond, interconversion of ring pucker, etc.

Examples of Chemical Shift Equivalent Nuclei

Ha

Rapid
Ha
Ha

exchange
Ha

Rapid
exchange

Coupling Constants
Magnetic Equivalence:

Nuclei must first be chemical shift equivalent

Must couple equally to each nucleus in every other set of chemically equivalent nuclei
i.

need to examine geometrical relationships

ii.

the bond distance and angles from each nucleus to another chemical set must be
identical

iii. Nuclei can be interchanged through a reflection plane passing through the nuclei
from the other chemical set and a perpendicular to a line joining the chemical shift
equivalent nuclei

Examples of Non-magnetically equivalent nuclei

Ha

Fa
Ha
Hb

Chemical shift
equivalent, but not
magnetic equivalent

C
Cl

Fa'

Ha'

Fa

Fa'
C

Hb'

Ha

Cl

Ha'
Ha'

Fa
Ha'

Jab Jab
3
Jab 3Jab
3

C
Ha

Fa'

JHaFa 3JHaFa
3
J
3J
3

JHaHc 3JHaHc
3
JHbHc 3JHbHc
3
JHaHc 3JHbHc
3
JHaHc 3JHbHc
3

Coupling Constants
Magnetic Equivalence:

Non-magnetically equivalent nuclei may lead to second order effects and very complex
splitting patterns

Second order effects will be discussed later

i.

Due to small chemical shift differences between coupled nuclei ( ~ J)

http://www.chem.wisc.edu/areas/reich/chem605/index.htm

Coupling Constants
Multiple Spin Systems
multiplicity (na+1)(nb+1)

What is the splitting

pattern for CH2?

Hb

Cl

Ha

Cl

Ha

1
11
121
1331
14641
1 5 10 10 5 1
1 6 15 20 15 6 1
1 7 21 35 35 21 7 1

Ha

JHb = 6 Hz
JHa = 7 Hz

JHb = 6 Hz

Coupling to Hb splits the

CH2 resonance into a
doublet separated by 6 Hz
Down-field resonance
split into quartet

up-field resonance
split into quartet

Coupling to Ha splits each

doublet into a quartet
separated by 7 Hz

Coupling Constants
What Happens to Splitting Pattern if J changes?
JHb = 7 Hz

JHa = 7 Hz

Looks like a pentet!

Intensities dont follow
Pascals triangle (1 4 6 4 1)

JHb = 6 Hz

JHa = 3 Hz

Looks like a sextet!

Intensities dont follow
Pascals triangle (1 5 10 10 5 1)

Occurs because of overlap of peaks within the splitting pattern

Coupling Constants
Coupling Constants Provide Connectivity Information
chemical shifts identify what functional groups are present

Hb

Cl

Ha

Cl

Ha

Ha

NMR Peaks for coupled nuclei

share the same coupling constants

CH3

CH

CH2
7 Hz

6 Hz

Integral:

6 Hz

7 Hz

6 Hz

6 Hz

7 Hz

7 Hz

Coupling Constants
Deconvoluting a spin system
determining the J-values
determining the multiplicities present

J coupling analysis:
i. Is the pattern symmetric about the center?
ii. Assign integral intensity to each line, outer lines assigned
to 1
iii. Are the intensities symmetric about the center?
iv. Add up the assigned intensities
Sum must be 2n, n = number of nuclei
Ex: sum = 16, n = 4
v. Separation of outer most lines is a coupling constant
Relative intensity determines the number of coupled
nuclei
Ex: intensity ratio: 1:2, 2 coupled nuclei
1st splitting pattern is a triplet (1:2:1)
vi. Draw the first coupling pattern
vii. Account for all the peaks in the spin pattern by repeatedly
matching the 1st splitting pattern
viii. Smallest coupling constant has been assigned

Coupling Constants
Deconvoluting a spin system
determining the J-values
determining the multiplicities present

J coupling analysis:
ix. Coupling pattern is reduced to the center lines of the 1st
splitting pattern.
x.

Repeat process

Ex: sum = 8, n = 3

Ex: intensity ratio: 1:1, 1 coupled nuclei

2nd splitting pattern is a doublet (1:1)

xi. Repeat until singlet is generated

Coupling Constants

Demo ACD C+H NMR Viewer software

first order coupling constants

Coupling Constants
Description of Spin System
each unique set of spins is assigned a letter from the alphabet

the total number of nuclei in the set are indicated as a subscript

the relative chemical shift difference is represented by separation in the alphabet

sequence

Large chemical shift differences are represented by AX or AMX (AX >> JAX)

Small chemical shift differences are represented by AB (AB < 5JAB)

Can also have mixed systems: ABX

magnetically in-equivalent nuclei are differentiated by a single quote: AAXX or

brackets [AX]2

Ha
Hx

Cl

Hx'

Cl

CH2ClCHCl2

CH3CH2R

CH3CH2F

A2X system

A3X2 system

A2M2X system

Ha'

[AX]2 or AAXX
system

AB system

J(AM)

J(AX)

J(AX)

J(AM)

M X

TMS

J(MX)

J(MX)

J(AM)

J(AX)

J(AM) = 4 Hz
J(AX)

J(AX) = 2.5 Hz
J(MX) = 6 Hz

Coupling Constants (J)

Observed splitting is a result of this electron-nucleus hyperfine interaction

Coupling is measured in hertz (Hz)

reversed

reversed

reversed

Range from 0.05 Hz to thousands of Hz

Can be positive or negative
1
o
JC-H and many other one-bond coupling are positive
JA-X is negative if are opposite sign

JH-H in sp3 CH2 groups are commonly negative

JH-H is always positive

For an AX system, JAX is negative if the

energy of the A state is lower when X has
the same spin as A ( or )
The spin states and transitions are swapped

Coupling Constants (J)

Measure the Relative Sign of Coupling Constants

Multiple experimental approaches (different NMR pulse sequences) or

simulations

E. COSY two-dimensional
NMR experiment
cross peaks identify which
chemical shifts are coupled

Coupling Constants (J)

Measure the Relative Sign of Coupling Constants

The cross-peak patterns identifies the coupling constant sign and

magnitude

Based on the slopes of the diagonal

line drawn through coupling pattern
3

JAX and 3JBX have the same sign

JAB opposite sign of 3JAX and 3JBX

Yellow-highlighted
regions are expanded

Coupling Constants (J)

Magnitude of the splitting is dependent on:

Number of bonds

JAB 9.4 Hz
4
JAC 1.1 Hz
5
JAB 0.9 Hz
3

Bond order (single, double triple)

JHH 8 Hz

JHH 11.6 & 19.1 Hz

JHH 9.1 Hz

Angles between bonds

trans 3JHH ~ 17 Hz

cis 3JHH ~10 Hz

geminal 2JHH ~2.5 Hz

Coupling Constants (J)

Magnitude of the splitting is dependent on:

dihedral angle

Fixed or average conformation

Coupling Constants (J)

Magnitude of the splitting is dependent on:

Cyclohexanes dihedral angles

Fixed or average conformation

Jaa 9-12 Hz
3
Jee or 3Jea 3-4 Hz
3

Jaa >> 3Jee,3Jea

Dual Karplus curves for

the axial and equatorial
protons

Coupling Constants (J)

Magnitude of the splitting is dependent on:

Cyclohexanes dihedral angles

examples

Coupling Constants (J)

Magnitude of the splitting is dependent on:

Cyclopentanes dihedral angles

Fixed or average conformation

Coupling Constants (J)

Magnitude of the splitting is dependent on:

Comparison between Cyclohexanes and Cyclopentanes

In chair cyclohexane, only one vicinal

In cyclopentane, two or three vicinal

coupling can be large (>7 Hz)

coupling can be large (>7 Hz)

Because of range of cyclopentane conformations, vicinal couplings are

variable: Jcis > Jtrans and Jcis > Jtrans
Only in rigid cyclopentanes can a stereochemistry be defined: Jcis > Jtrans

Coupling Constants (J)

Magnitude of the splitting is dependent on:

Cyclobutanes are flatter than cyclopentanes, so: Jcis > Jtrans

unless structure features induce strong puckering of the ring or electronegative

substituents are present

Cyclopropanes are rigidly fixed, so Jcis > Jtrans is always true

Coupling Constants (J)

Magnitude of the splitting is dependent on:

Orientation

unless structure features induce strong puckering of the ring or

electronegative substituents are present

Since methyl groups can freely rotate,

the observed coupling is the average of
the three individual coupling constants

Internal hydrogen bonds may lead to constrained conformations and

distinct different coupling constants

Coupling Constants (J)

Magnitude of the splitting is dependent on:

Electronegativity of Substituents

JH-H coupling constant decreases

as electronegativity increases

JH-H decreases even more with

two electronegative substituents
3

Coupling Constants (J)

Magnitude of the splitting is dependent on:

Electronegativity of Substituents

JH-H coupling constant decreases as

electronegativity of substituents
increases for cycloalkenes

JH-H coupling constant decreases as

electronegativity of substituents
increases for alkenes

Coupling Constants (J)

Magnitude of the splitting is dependent on:

Ring Size

Coupling constants decrease as ring size gets smaller

Coupling constants also decrease as ring is formed and gets smaller

Coupling Constants (J)

Magnitude of the splitting is dependent on:

Bond order

Coupling constant decreases as bond order decreases

JH-H = 8.65 x (n bond order) + 1.66

Heterocycles

Heterocycles have smaller coupling constants compared to hydrocarbons

systems

Coupling Constants (J)

Magnitude of the splitting is dependent on:

Proportional to ab
1

JC-H 125 Hz
JN-H 95 Hz

s character of bonding orbital

Increases with increasing s-character in C-H bond

JF-H 48.2 Hz

Coupling Constants (J)

Magnitude of the splitting is dependent on:

Attenuated as the number of bonds increase

Usually requires conjugated systems (aromatic, allylic, propargylic,

allenic) or favorable geometric alignment (W-coupling)

Not usually seen over more than 4 to 5 bonds (acetylenes and allenes)

Coupling Constants (J)

Magnitude of the splitting is dependent on:

Geminal protons (H-C-H) fall into two major groups

Unstrained sp3 CH2 protons: 2JH-H -12 Hz

Vinyl sp2 CH protons: 2JH-H 2 Hz

Coupling Constants (J)

Magnitude of the splitting is dependent on:

Geminal protons coupling constants are effected by the electronic effects of

substituents

Note:
opposite
trend

Based on the interaction between the filled and empty orbitals of the CH 2
fragment

Coupling Constants (J)

Magnitude of the splitting is dependent on electronic effects:

In acyclic and unstrained ring systems: 2JH-H ~ -10 to -13 Hz

When CH2 is substituted with a -acceptor, like carbonyl or cyano coupling
becomes more negative: 2JH-H ~ -16 to -25 Hz

Reliable and can help with structure assignments

Conjugated aryl, alkene and alkyne substituents also makes coupling

becomes more negative

Coupling Constants (J)

Magnitude of the splitting is dependent on electronic effects:

In unsaturated carbons: 2JH-H ~ 2.5 Hz

Electronegative substituents (F,O) behave as -acceptors with a negative
effect with 2JH-H close to zero
Electropositive substituents (Si, Li) behave as -donors with a negative
effect with 2JH-H

Oxygen substituents can behave as a strong -acceptor and strong -donor

(lone pair), both positive effects leading to a large 2JH-H or as a strong pacceptor leading to large negative coupling

Coupling Constants (J)

Magnitude of the splitting is dependent on electronic effects:

Summary of effects, and acceptors have opposite effects on coupling, as

do and donors

Coupling Constants (J)

Coupling Constants (J)

Coupling Constants (J)

Coupling Constants
Weak coupling or first-order approximation

Up to now, we have assumed the frequency difference (chemical shift) between the
coupled nuclei is large
i.

>> J

Second order effects come into play when this assumption is no longer valid
i.

< 5J

Second order effects lead to very complex splitting patterns that are difficult, if not
impossible to interpret manually and leads to incorrect chemical shifts and coupling
constants

Interpreting NMR spectra with second-order effects usually requires software

Coupling Constants (J)

Second-Order Effects (Strong Coupling)
occurs when chemical shift differences is similar in magnitude to coupling
constants (/J < 5)

chemical shifts and coupling constants have similar energy and intermingle

results from mixing of the equivalent and spin states

none of the transitions are purely one nuclei

described by quantum mechanical wave functions

AB spin system

Coupling Constants (J)

Second-Order Effects (Strong Coupling)

perturbs peak intensity and position

AB spin system

as chemical shift differences decrease, intensity of outer lines become

weaker and internal lines become stronger

the multiplet leans towards each other (roof effect) which increases as
chemical shift difference decreases

Coupling Constants (J)

Second-Order Effects (Strong Coupling)

becomes easier to interpret at higher magnetic field strengths

Higher field increases /J

Coupling Constants (J)

Second-Order Effects (Strong Coupling)
hierarchy of coupling constants with increasing second-order effects
1. AX and all other first order systems (AX2, AMX, A3X2, etc.)
2. AB
i.

Line intensities start to lean

ii.

J can be measured, can be calculated

3. AB2
i.

Extra lines

ii.

Both J and have to be calculated

4. ABX, ABX2, ABX3

i.

JAB can be measured, everything else requires calculation

5. ABC
i.

Both J and have to be determined from computer simulation

6. AAXX
i.

Do not become first order even at high magnetic fields

ii.

Both J and have to be determined from computer simulation

7. AABB
8. AABBX
9. Etc.

Coupling Constants (J)

Second-Order Effects (Strong Coupling)
general effect of strong couplings on NMR spectra
1. Line intensities are no longer integral ratios, no longer follow Pascals
triangle
2. Line positions are no longer symmetrically related to chemical shift position
i.

Multiplet center may no longer be chemical shift (AB and higher)

3. Some or all coupling constants can no longer be obtained from the line
separations (ABX and higher)
4. The signs of coupling constants affect the line positions and intensities
(ABX and higher)
5. Additional lines over the number predicted by simple coupling rules appear
i.

Peaks with intensities of 2 or more are split into individual components

More lines then the

expected triplet for
the boxed CH2 pair

Coupling Constants (J)

Second-Order Effects (Strong Coupling)
general effect of strong couplings on NMR spectra
6. Coupling between equivalent nuclei (JAA or JXX) affects line count and
position
i.

Second order effects appear even if /J is large for groups of magnetically

non-equivalent protons with identical chemical shifts which are coupled

i.

Do not get simpler at higher fields

7. Computer analysis becomes mandatory to extract accurate J and values

(ABC and higher)
8. Ultimately spectra become so complex that the only useful information is
integration, chemical shift and general appearance.

Coupling Constants (J)

Second-Order Effects
as the chemical shifts coalesce

intensity of outer lines decrease

inner peaks eventually collapse to

singlet

nuclei become chemically and

magnetically equivalent

Weaker outer lines may

be overlooked and
interpreted as a doublet
May be misinterpreted
as a quartet

AB spin system

Coupling Constants (J)

Second-Order Effects (AB)
analysis of second-order splitting patterns

remember: resonance positions are also perturbed

separation between outer lines and inner lines (a-b, c-d) yields coupling constant

JAB = (a-b) = (c-d)

true chemical shift is not the doublet centers

center = (b+c)
AB = (a-d) (b-c)
A = center + AB
B = center - AB

Coupling Constants (J)

Coupling Constants (J)

Second-Order Effects (AB2)
as the chemical shifts coalesce

line intensities no longer follow simple rules

arithmetic average of the line positions no

longer give true chemical shifts

JAB can still be measured directly from

spectrum

none of the line separation correspond to

JAB

additional lines appear

AB2 spin system

Note:
splitting of
intense lines

Coupling Constants (J)

Second-Order Effects (AB2)
four A lines 1 4 and four B lines 5 8 and the very weak combination line 9
calculation of A, B, and JAB is simple:

how to report an AB2 spin system in a journal manuscript:

report the two chemical shifts as an AB2 multiplete (m):

2.63, 2.69 (AB2m, 3H, JAB = 12.2 Hz)

Coupling Constants (J)

Second-Order Effects (AB2)
unique features of second-order splitting pattern for AB2 system

Spectrum depends only on the ratio /J

lines 1 to 4 correspond to the one proton part (A)

lines 5 to 8 correspond to the two-proton part (B2)

line 5 (5) is the most intense line

lines 5 and 6 often do not split up

when /J << 1, the spectrum appears nearly symmetrical

lines 1,2, 8 1, 2 ,8) become very weak

looks like a distorted triplet with 1:10:1 area ratio

JAB and JBB do not affect the spectrum

Coupling Constants (J)

Second-Order Effects (ABX)
most complex spin-system that can still be manually analyzed
ABX has a common appearance

AB unsymmetrical 8-line pattern that integrates to 2 protons

AB 4 doublets with the same separation JAB with strong leaning

X symmetric 6-line pattern that integrates to 1 proton

X 5th and 6th lines are small and not often seen, apparent doublet of doublet

JAB and X are directly measurable from spectrum

X - center

AB

JAX, JBX, A and B need to be calculated

of peaks

Coupling Constants (J)

Second-Order Effects (ABX)
Many ABX patterns are sufficiently close to AMX (AB >> JAB)

first-order solution has an excellent chance of being correct

A & B doublet of doublet

separation is JAX & JBX
Center doublets
and get AB pattern

First, identify the distorted doublet of doublets for both A and B

Remove the splitting (identify the center of each doublet), which leaves an AB pattern
Solve AB pattern as before to get JAB, A, and B

large errors when JAX and JBX are very different or AB small compared to JAB

Coupling Constants (J)

Second-Order Effects (ABX)
Correct analysis of ABX patterns

Reverse the order of extracting coupling constants to approximate solution

Identify the two AB quartets

Jab+ = Jab-

First, identify the two AB quartets

separation between the four pairs of lines are identical

tall inner line associated with shorter outer line (leaning)

Coupling Constants (J)

Second-Order Effects (ABX)
Correct choice of ab quartet

Incorrect choice of ab quartet

Coupling Constants (J)

Second-Order Effects (ABX)
Solve the two ab quartets

Treat as normal AB patterns and obtain four chemical shifts (a+,b+,a-,b-)

Dont know which half is a and which is b - two possible solutions

Coupling Constants (J)

Second-Order Effects (ABX)
Solution 1 and Solution 2 depends on the relative sign of JAX and JBX

Solution 1: JAX and JBX same sign

Solution 2: JAX and JBX different sign

Swap the a & b labels

Coupling Constants (J)

Second-Order Effects (ABX)
Which solution is the correct one?
Several criteria can be used:
1. Magnitude of the couplings one solution may give dubious (very large or very
small) couplings
2. Signs of coupling constants the signs can sometimes be predicted and rule
out a solution

all vicinal 3J couplings are positive,

geminal 2J couplings at sp3 carbons are usually negative

CHXCHAHB JAX and JBX have the same sign

CHACHBHX JAX and JBX have different signs

Analysis of the X-part the intensities of the lines in the X-part are always
different most reliable way to identify the correct solution

Two different X patterns

depending on relative sign of
JAX and JBX

Coupling Constants (J)

Second-Order Effects (ABX)
Effective of relative sign of JAX and JBX on AB pattern

Solution 1
JAX and JBX same sign

Solution 2
JAX and JBX different sign

Coupling Constants (J)

Second-Order Effects (ABX)
AB pattern from ABX spin
system as a function of
changing AB

Coupling Constants (J)

Second-Order Effects (ABX)
AB pattern from ABX spin
system as a function of
the relative sign and
Magnitude of JAX and JBX

JAX and JBX same sign

JAX and JBX different sign

Coupling Constants (J)

Demo ACD C+H NMR Viewer software

second order coupling constants