NMR

Spectrosc
opy

Fall
1
1
0
2

CHEM 430

NMR - The
Coupling
Constant

41

FIRST ORDER SPECTRA

For a spectrum to be 1st order, the between the chemical shifts

of any given pair of nuclei must be much larger than the value of
the coupling constant J between them:
J > 10
1st order spectra exhibit the following characteristics:
Spin spin multiplets are centered on the resonance frequency.
Spacings between adjacent components of a spinspin multiplet
= J.
Multiplicities that result from coupling exactly reflect the n + 1
rule for I =
The intensities of spinspin multiplets correspond to the
coefficients of the binomial expansion given by Pascals triangle
for spin- nuclei
CHEMchemical
430 NMR
Nuclei with the same
shift do not split
2 each other, even
Spectroscopy
when the coupling constant between them is nonzero.

NMR - The
Coupling
Constant

41

FIRST ORDER SPECTRA

When the chemical shift difference is less than about 10 times J,

2nd order effects appear in the spectrum, including deviations in
intensities from the binomial pattern and other exceptions from
the preceding characteristics.
Pople notation:
Nuclei that have a 1st order relationship are represented by letters
that are far apart in the alphabet (AX)
Nuclei that are close in chemical shift and may exhibit a second-

order relationship are represented by adjacent letters (AB)

Nuclei in the middle of AX are represented as M

Higher field spectrometers > 300 MHz increase (i.e. 1 ppm

represents a greater number of Hz) and minimize 2 nd order effects
CHEM 430 NMR
Spectroscopy

NMR - The
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Constant

41

FIRST ORDER SPECTRA

AB Spin System - 1st to 2nd order

/J = 0.4

/J = 1

/J = 4

/J = 15

CHEM 430 NMR

Spectroscopy

NMR - The
Coupling
Constant

41

FIRST ORDER SPECTRA

AB2 Spin System 1st to 2nd order

/J = 0.4

/J = 1

/J = 4

/J = 15

CHEM 430 NMR

Spectroscopy

NMR - The
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Constant

42

CHEMICAL AND MAGNETIC

EQUIVALENCE

In addition to meeting the requirement that n / J > 10 , 1st order

spectra must pass a symmetry test.
Any two chemically equivalent nuclei must have the same coupling
constant to every other nucleus.
Nuclear pairs that fail this test are said to be magnetically
nonequivalent, and their spectral appearance is 2nd order

CHEM 430 NMR

Spectroscopy

NMR - The
Coupling
Constant

42

CHEMICAL AND MAGNETIC

EQUIVALENCE

Symmetry
Nuclei are chemically equivalent if they can be interchanged by
a symmetry operation of the molecule.
Thus the two protons in 1,1- difluoroethene or in difluoromethane

may be interchanged by a 180 rotation. Nuclei that are

interchangeable by rotational symmetry are said to be homotopic.
Rotation about CC single bonds is so rapid that the chemist

rarely considers the fact that the three methyl protons in CH 3CH2Br
are not symmetrically equivalent (dynamic effect)

CHEM 430 NMR

Spectroscopy

NMR - The
Coupling
Constant

42

CHEMICAL AND MAGNETIC

EQUIVALENCE

Symmetry
Nuclei related by a plane of symmetry are called enantiotopic, provided
there is no rotational axis of symmetry.
For example, the protons in BrClCH2 are chemically equivalent and

enantiotopic because they are related by the plane of symmetry containing

C, Br, and Cl.

If the molecule is placed in a chiral environment, (using a solvent composed

of an optically active material or by placing the molecule in the active site

of an enzyme) as represented by a small hand placed to one side of BrClCH 2
the protons are no longer equivalent because the hand is a chiral object.
CHEM 430 NMR
Spectroscopy

NMR - The
Coupling
Constant

42

CHEMICAL AND MAGNETIC

EQUIVALENCE

Symmetry
Because the plane of symmetry is lost in a chiral environment,
the nuclei are not enantiotopic and have become chemically
nonequivalent ( no symmetry operation can interchange them).
The term enantiotopic was coined because replacement of one

proton of the pair by another atom or group, such as deuterium,

produces the enantiomer

CHEM 430 NMR

Spectroscopy

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Coupling
Constant

42

CHEMICAL AND MAGNETIC

EQUIVALENCE

Symmetry
Enantiotopic or homotopic protons need not be on the same carbon. For
example the alkenic protons in cyclopropene are homotopic, but those in
3- methylcyclopropene are enantiotopic.
Chemically equivalent nuclei (homotopic or enantiotopic) are

represented by the same letter in the spectral shorthand of Pople.

Cyclopropene is A2X2, as is difluoromethane, since the two fluorine atoms

have spins of

The ring protons of 3-methylcyclopropene constitute an AX 2 group.

CHEM 430 NMR
Spectroscopy

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NMR - The
Coupling
Constant

42

CHEMICAL AND MAGNETIC

EQUIVALENCE

Symmetry
To be magnetically equivalent, two nuclei must be chemically
equivalent and have the same coupling constant to every other
nucleus.
This test is more stringent than that for chemical equivalence,

because it is necessary to go beyond considering just the overall

symmetry of the molecule.
For example, in CH2F2 each of the two hydrogens has the same

coupling to a specific fluorine atom because both hydrogens

have the same spatial relationship to that fluorine.
Consequently, the protons are chemically and magnetically
equivalent - A2X2.

CHEM 430 NMR

Spectroscopy

11

NMR - The
Coupling
Constant

42

CHEMICAL AND MAGNETIC

EQUIVALENCE

Symmetry
Examples that once seemed simple:
p-nitrotoluene
On first inspection, like CH2F2, it has a plane of symmetry

NO2

JabJab

Ha

Ha'

Hb

Hb'
CH3

However, on careful inspection the coupling of what would be two

chemically identical nuclei (Ha and Ha) is different to Hb so these are

magnetically non-equivalent
CHEM 430 NMR
Spectroscopy

12

NMR - The
Coupling
Constant

42

CHEMICAL AND MAGNETIC

EQUIVALENCE

Symmetry
Examples that once seemed simple:
1,1-difluroethene
Like the previous example, the molecule has a plane of symmetry

JaFJbF

Here, the fluorines are spin-active (1/2), so each hydrogen is

coupled differently to Fa so these are magnetically nonequivalent
CHEM 430 NMR
Spectroscopy

13

NMR - The
Coupling
Constant

42

CHEMICAL AND MAGNETIC

EQUIVALENCE

Symmetry
Why is this important?
Any spin system that contains nuclei that are chemically
equivalent but magnetically nonequivalent is, by definition, 2 nd
order.
Moreover, raising the magnetic field cannot alter basic

structural relationships between nuclei, so that the spectrum

remains second order at the highest accessible fields.
Nuclei that do not have the same chemical shift (anisochronous)

also are magnetically nonequivalent because they resonate at

different resonance frequencies (chemical shift criterion).

CHEM 430 NMR

Spectroscopy

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NMR - The
Coupling
Constant

42

CHEMICAL AND MAGNETIC

EQUIVALENCE

Symmetry
Isochronous nuclei that are magnetically non-equivalent by having
unequal couplings to another nucleus are said to fail the coupling
constant criterion.
Nuclei that are chemically equivalent but not magnetically

equivalent are given the same letter in the Pople notation, but one
is denoted by a prime
Thus 1,1-difluoroethene is a AAXX system

CHEM 430 NMR

Spectroscopy

15

NMR - The
Coupling
Constant

42

CHEMICAL AND MAGNETIC

EQUIVALENCE

Symmetry
Spectra for these systems are complex 1H spectrum of 1,1difluoroethene:

CHEM 430 NMR

Spectroscopy

16

NMR - The
Coupling
Constant

42

CHEMICAL AND MAGNETIC

EQUIVALENCE

Symmetry
Another example 1H spectrum of 1,2-dichlorobenzene:

CHEM 430 NMR

Spectroscopy

17

NMR - The
Coupling
Constant

42

CHEMICAL AND MAGNETIC

EQUIVALENCE

Symmetry
Even open- chain systems such as ClCH2CH2OH contain
magnetically nonequivalent spin systems:
A 1st order spectrum would
have comprised two 1: 2: 1
triplets (not case here) and
instead of three peaks in each
resonance, there are four
(look to sides of center
resonance)

CHEM 430 NMR

Spectroscopy

18

NMR - The
Coupling
Constant

42

CHEMICAL AND MAGNETIC

EQUIVALENCE

Symmetry

CHEM 430 NMR

Spectroscopy

19

NMR - The
Coupling
Constant

43

SIGNS AND MECHANISMS

Fermi Contact Interaction

Spinspin coupling arises because information about nuclear spin
is transferred from nucleus to nucleus via the electrons.
Both nuclei and electrons are magnetic dipoles, whose mutual

interactions normally are described by the pointdipole

approximation (as used by McConnell to describe diamagnetic
anisotropy)
Fermi found that this approximation breaks down when dipoles

are very close (comparable to the radius of a proton).

Under these circumstances, when the nucleus and electron in

essence are in contact, their interaction is described by a new

mechanism, the Fermi contact term.
CHEM 430 NMR
Spectroscopy

20

NMR - The
Coupling
Constant

43

SIGNS AND MECHANISMS

Fermi Contact Interaction

The energy of the interaction is proportional to the gyromagnetic
ratios of the nucleus and of the electron, the scalar (dot) product
of their spins (I for a nucleus, S for an electron), and the probability
that the electron is at the nucleus (the square of the electronic
wave function evaluated with zero distance from the nucleus): .
EFC n eI S 2(0)

CHEM 430 NMR

Spectroscopy

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NMR - The
Coupling
Constant

43

SIGNS AND MECHANISMS

Fermi Contact Interaction

Because the nuclear and electronic gyromagnetic ratios have
opposite signs , the more stable arrangement is when the
nucleus and the electron are antiparallel (spins paired):

Nuclear spin

electron spin

Nuclear spin

electron spin

Energy

CHEM 430 NMR

Spectroscopy

22

NMR - The
Coupling
Constant

43

SIGNS AND MECHANISMS

Fermi Contact Interaction

Here, a single bond (two electrons) joins two spin-active
nuclei: 13C-1H
The bonding electrons will tend to avoid one another, if one

is near the 13C nucleus (in this example) the other will be
near the 1H nucleus
By the Pauli principle, these electrons must be opposite in

spin
The Fermi model then predicts that the most stable

condition 13
between the two nuclei must 1be one in which
C spin
H spin
they too are opposite in spin:
electrons opposite in spin
CHEM 430 NMR
Spectroscopy

23

NMR - The
Coupling
Constant

43

SIGNS AND MECHANISMS

Fermi Contact Interaction

When one spin slightly polarizes another spin oppositely the
coupling constant J between the spins has a positive sign by
convention .
A negative coupling occurs when spins polarize each other in the

same (parallel) direction.

Qualitative models indicate that coupling over two bonds, as in H

CH, is negative, while coupling over three bonds, as in HCC

H is positive.
There are numerous exceptions to this qualitative model, but it is

useful in understanding that J has sign as well as magnitude.

CHEM 430 NMR

Spectroscopy

24

NMR - The
Coupling
Constant

43

SIGNS AND MECHANISMS

Fermi Contact Interaction

There are many variations of the subscripts and superscripts
associated with J constants
In general, the superscript numeral to the left of J is the number of

intervening bonds through which the coupling is taking place

J is a coupling constant operating through two bonds - geminal

3
J is a coupling constant operating through three bonds vicinal
4
J is a coupling constant operating through four bonds long
range
2

Subscripts to the right of J can be used to show the type of

coupling, such as HH for homonuclear between protons or HC for

heteronuclear between a carbon and proton
Often, this subscript will be used to order the various J-constants

within a complex multiplet: J1, J2, J3, etc. or JAB, JBC, JAC
CHEM 430 NMR
Spectroscopy

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NMR - The
Coupling
Constant

43

SIGNS AND MECHANISMS

Fermi Contact Interaction

High resolution NMR spectra normally are not dependent on the
absolute sign of coupling constants.
Simultaneous reversal of the sign of every coupling constant in

a spin system results in an identical spectrum.

Many spectra, however, depend on the relative signs of

component couplings.
For example, the general ABX spectrum is determined in part by

three couplings, JAB, JAX, and JBX

Different spectra can be obtained when JAX and JBX have the

same sign from when they have opposite signs even when the
magnitudes are the same.
CHEM 430 NMR
Spectroscopy

26

NMR - The
Coupling
Constant

44

COUPLINGS OVER ONE BOND

The one- bond coupling between

C and 1H is readily measured

from the 13C spectrum when the decoupler is turned off

Although it complicates routine

13

C interpretation, this coupling

can provide useful information and illustrates several important
principles.
13

Because a p orbital has a node at the nucleus, only electrons in

s orbitals can contribute to the Fermi coupling mechanism (s

orbitals have a maximum in electron density at the nucleus).
For protons, all electrons reside in the 1s orbital, but, for other

nuclei, only that proportion of the orbital that has s character

can contribute to coupling.

CHEM 430 NMR

Spectroscopy

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NMR - The
Coupling
Constant

44

COUPLINGS OVER ONE BOND

When a proton is attached to an sp 3 carbon atom (25% s

character), 1JHC is about half as large as that for a proton attached

to an sp carbon atom ( 50% s character).
These numbers define a linear relationship between the %-s

character of the carbon orbital and the one- bond coupling:

%-s(CH) = 0.2 J(13CH)
JHC ethane = 125 Hz (sp3)
1J
2
HC ethene = 156 Hz (sp )
1J
HC ethyne = 249 Hz (sp)
1

The zero intercept of this equation indicates that there is no

coupling when the s character is zero, in agreement with the Fermi

contact model.
CHEM 430 NMR
Spectroscopy

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NMR - The
Coupling
Constant

44

COUPLINGS OVER ONE BOND

The 1JCH coupling ranges from about 100 to 320 Hz, and may be

interpreted in terms of the J s relationship

The coupling constant in cyclopropane (162 Hz) demonstrates that the

carbon orbital to hydrogen is approximately sp 2 hybridized!

Other examples include tricyclopentane (144 Hz, 29% s, sp 2.4), cubane

(160 Hz, 32% s, sp2) and quadricyclane (179 Hz, 36% s, sp1.8) .
Although the Js relationship works well for hydrocarbons not as

applicable to polar bonds.

CHEM 430 NMR
Spectroscopy

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NMR - The
Coupling
Constant

44

COUPLINGS OVER ONE BOND

For other nuclei variations in the effective nuclear charge and

hybridization effects, may alter the coupling constants.

Just as the resonance frequency of a nucleus is proportional to its

gyromagnetic ratio , the coupling constant between two nuclei, as

noted above, is proportional to the product of both gyromagnetic
ratios.
Nuclei with very small gyromagnetic ratios, such as

15

N, tend to

have correspondingly small couplings.

N has a negative sign, whereas 1H and 13C are positive.
Therefore 1JNH between 15N and hydrogen have a negative sign

For

15

One bond couplings have been studied for other nuclei but are

more complex
CHEM 430 NMR
Spectroscopy

30

NMR - The
Coupling
Constant

44

COUPLINGS OVER ONE BOND

CHEM 430 NMR

Spectroscopy

31

NMR - The
Coupling
Constant

45

GEMINAL COUPLINGS

By the Fermi model for geminal coupling (HCH) 2J is usually

negative
Geminal coupling (HCH) cay be measured directly from the

spectrum
when
the
coupled
nuclei
are
chemically
nonequivalent, (the AB or AM part of an ABX, AMX, ABX 3
spectrum).
If the relationship is 1st order (AM), the coupling may be

measured by inspection. In 2nd order cases (AB), the spectrum

must be simulated computationally, unless the two spins are
isolated (a two- spin system)
When

nuclei are chemically equivalent but magnetically

nonequivalent (as in the AA' part of an AA'XX' spectrum) their
coupling constant is accessible by computational methods
CHEM 430 NMR
Spectroscopy

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NMR - The
Coupling
Constant

45

GEMINAL COUPLINGS

Here, a intervening atom (usually a spin-inactive

C)
communicates spin information between the two interacting
nuclei
12

The Fermi model then predicts that the most stable condition

between the these two geminal nuclei must be one in which they
are parallel in spin:
C is spin inactive

C is spin inactive

12

H spin

12

H spin

H spin

H spin

13

CHEM 430 NMR

Spectroscopy

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NMR - The
Coupling
Constant

45

GEMINAL COUPLINGS

IMPORTANT
Splittings are not observed between coupled nuclei when they are
magnetically equivalent, but the coupling constant may be
measured by replacing one of the nuclei with deuterium.
For example, in CH2Cl2- the geminal H C D coupling is seen as

the spacing between the components of the 1: 1: 1 triplet

(deuterium has a spin of 1).
Since coupling constants are proportional to the product of the

gyro-magnetic ratios of the coupled nuclei, J( HCH) may be

calculated from J(HCD):

CHEM 430 NMR

Spectroscopy

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NMR - The
Coupling
Constant

45

GEMINAL COUPLINGS

As the H-C-H decreases, the amount of electronic interaction

between the two orbitals increases, the electronic spin

correlations also increase and J becomes larger (more negative)
H
H

H-C-H 109o
2
JHH = -12-18 Hz

In general:
40
JHH

H
H

H
H

H-C-H 118o
2
JHH = -4.3 Hz

H-C-H 120o
2
JHH = +0-3 Hz

CHEM 430 NMR

Spectroscopy

20

90 100

35

110

120

NMR - The
Coupling
Constant

45

GEMINAL COUPLINGS

Variations in J also result from hybridization and ring size

As ring size decreases, C-C-C decreases, along with p-

character; the resulting H-C-H increases, along with the

corresponding s -character J becomes smaller
H

JHH (Hz) = -2

-4

H
C

H
2

-9

-11

CHEM 430 NMR

Spectroscopy

-13

-9 to -15

36

NMR - The
Coupling
Constant

45

GEMINAL COUPLINGS

Electron withdrawal by induction tends to make the coupling

constant more positive - for alkanes the negative coupling thus

decreases in absolute value (becoming less negative)
CH4 -12.4 to CH3OH -10.8 Hz
CH3I -9.2 to CH2Br2 -5.5 Hz
Electron donation makes the coupling more negative

CH4, -12.4 to TMS -14.1 Hz

Analogous substitution on sp2 carbon changes the coupling

profoundly:

CHEM 430 NMR

Spectroscopy

37

NMR - The
Coupling
Constant

45

GEMINAL COUPLINGS

These effects of withdrawal or donation of electrons through the

-bonds (induction) can be augmented or diminished by effects such as hyperconjugation.

Lone pairs of electrons can donate electron density and make 2J

more positive, whereas the orbitals of double or triple bonds can

withdraw electrons and make 2J less positive (or more negative).
The above-mentioned large increase in the geminal coupling of

imines or formaldehyde compared with ethene results from

reinforcement of the effects of withdrawal and donation

CHEM 430 NMR

Spectroscopy

38

NMR - The
Coupling
Constant

45

GEMINAL COUPLINGS

These effect of -withdrawal occurs for carbonyl, nitrile, and

aromatic groups as in the values for acetone (14.9 Hz),

acetonitrile ( 16.9 Hz), and dicyanomethane ( 20.4 Hz).

The effect is some-what reduced by free rotation in open-chain

systems, so that particularly large effects are created by

constraints of rings:

-donation by lone pairs makes J more positive. This effect also

explains the difference in the geminal couplings of threemembered rings: cyclopropane and oxirane
CHEM 430 NMR
Spectroscopy

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NMR - The
Coupling
Constant

45

GEMINAL COUPLINGS

Remember

splittings are not observed for magnetically

equivalent nuclei (like the 4 hydrogens on CH 4) ; the 2J values in
this table are used as reference values and generated by
observing the 2JHD for the deuterated analog of these compounds
(top page 92 in text).

CHEM 430 NMR

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NMR - The
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Constant

45

GEMINAL COUPLINGS

Geminal couplings between protons and other nuclei also have

been studied.
The HC13C coupling responds to substituents in much the

same way as does the HCH coupling; values are smaller, due
to the smaller of 13C.
Unlike the HCH case, the HC13C geminal coupling pathway

can include a double or triple bond; such couplings can be

useful to determine stereochemistry:

CHEM 430 NMR

Spectroscopy

41

NMR - The
Coupling
Constant

45

GEMINAL COUPLINGS

The 2JHCN between hydrogen and

N strongly depends on the

presence and orientation of the nitrogen lone pair.

15

JHCN is a useful structural diagnostic for synanti isomerism in

imines, oximes, and related compounds as the HC15N coupling
in imines is larger and negative when the proton is cis to the
lone pair but smaller and positive for a proton trans to the lone
pair:
2

The cis relationship between the nitrogen lone pair and

hydrogen also is found in heterocycles such as pyridine 2JHCN

-10.8.
CHEM 430 NMR
Spectroscopy

42

In saturated amines with rapid bond rotation values typically are

NMR - The
Coupling
Constant

45

GEMINAL COUPLINGS

J between 15N and 13C follow a similar pattern and also can be
used for structural and stereochemical assignments.
2

The carbon on the same side as the lone pair (syn) in imines

again has a larger, negative coupling (- 11.6 Hz). The antiisomer has a 2JCCN of 1.0 Hz.
Likewise, the two indicated carbons in quinoline have couplings

differentiated by their geometry - as one is syn and the other

anti to the nitrogen lone pair.

CHEM 430 NMR

Spectroscopy

43

NMR - The
Coupling
Constant

45

GEMINAL COUPLINGS

JHCP between 31P and hydrogen also have been exploited

stereochemically.
2

The maximum positive value of 2JHCP is observed when the HC

bond and the phosphorus lone pair are eclipsed (syn), and the
maximum negative value when they are orthogonal or anti.

The situation is similar to that for couplings between hydrogen

and 15N, but signs are reversed as a result of the opposite signs
of the gyromagnetic ratios of 15N and 31P.
The coupling also is structurally dependent, as it is larger for

P(III) than for P(V):

CHEM 430 NMR

27
Hz for (CH3)3P
Spectroscopy

and 13.4 Hz44

for (CH3)3P=O.

NMR - The
Coupling
Constant

45

GEMINAL COUPLINGS

Geminal H C F couplings are usually close to for an sp 3 carbon

(47.5 Hz for CH3CH2F) and for an sp2 carbon (84.7 Hz for

CH2=CHF).
Geminal FCF couplings are quite large for saturated carbons

(240 Hz for 1,1-difluorocyclohexane), but less than 100 Hz for

unsaturated carbons (35.6 Hz for CH2=CF2).

CHEM 430 NMR

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NMR - The
Coupling
Constant

46

VICINAL COUPLINGS

Coupling constants between protons over three bonds have

provided the most important early stereochemical application of

NMR spectroscopy - vicinal coupling
As with geminal coupling, the overall lowest energy spin state is

one where the 1H nuclei and electron spins are paired (12C is spin
inactive)
Observe the two possible spin interactions:

CHEM 430 NMR

Spectroscopy

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NMR - The
Coupling
Constant

46

VICINAL COUPLINGS

Observe that the orbitals must overlap for this communication

to take place weaker J-constants

To communicate spin information, one additional flip must

take place, and the J-values are usually positive

The magnitude of the interaction, it can readily be observed, is

greatest when the orbitals are at angles of 0o and 180o to one

another:

0o dihedral angle
180o dihedral angle
CHEM 430 NMR
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NMR - The
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Constant

46

VICINAL COUPLINGS

In 1961, Karplus derived a mathematical relationship between

JHCCH and dihedral HCCH .

The cos2 relationship results from strong coupling when orbitals

are parallel. They can overlap at the syn-periplanar or antiperiplanar geometries.

When orbitals are staggered or orthogonal , coupling is weak.
A and C are empirically determined constants; C and C usually

are neglected, as they are thought to be less than 0.3 Hz while A

and A imply that J is different at the syn and the anti-maximum
CHEM 430 NMR
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NMR - The
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Constant

46

VICINAL COUPLINGS

Unfortunately, these multiplicative constants vary from system

to system in the range 814 Hz and quantitative applications

cannot be transferred easily from one structure to another.
In general:

12
8
J (Hz)

6
4
2
0

45 90 135 180

CHEM 430 NMR

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NMR - The
Coupling
Constant

46

VICINAL COUPLINGS

In chair cyclohexane Jaa is large as aa is close to 180

Jee (0 5 Hz) and Jae (1 6 Hz) are small as ee and ae are close to 60
When cyclohexane rings are flipping between two chair forms, Jaa is

averaged with Jee to give a Jtrans in the range 4 9 Hz, and Jae is
averaged with Jea to give a smaller Jcis, still in the range 1 6 Hz.

In conformationally locked systems (no ring flip) the effect can be

used to assign stereochemistry

CHEM 430 NMR
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50

NMR - The
Coupling
Constant

46

VICINAL COUPLINGS

Further examples:
H

H
HH

Jaa = 10-14 Hz

180

Jee = 4-5 Hz

60

CHEM 430 NMR

Spectroscopy

Jae = 4-5 Hz

60

51

NMR - The
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Constant

46

VICINAL COUPLINGS

For alkenes 3Jtrans ( = 180o) is always larger than 3Jcis ( = 0o)

H

Jtrans = 11-18 Hz

180

Jcis = 6-15 Hz
0

Jtrans > 3Jcis > 2Jgem allows assignment of the vinyl system (AMX,
ABX or ABC spectrum) trivial
3

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52

NMR - The
Coupling
Constant

46

VICINAL COUPLINGS

For cyclic alkenes internal bond angles may affect 3Jcis

H

120o angle in H-C-C

bond reduces
overlap

Jtrans = 11-18 Hz

Jcis = 6-15 Hz
0

180

Jcis = 0-2

2-4

5-7

8-11

6-15 Hz

CHEM 430 NMR

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53

NMR - The
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Constant

46

VICINAL COUPLINGS

Despite the potentially general application of the Karplus

equation to dihedral angle problems, there are quantitative

limitations.
The 3J HCCH depends on the CC bond length or bond order,

the HCC valence angle, the electronegativity and orientation

of substituents on the carbon atoms in addition to the HCCH
dihedral angles.
A properly controlled calibration series of molecules must be

rigid (mono-conformational) and have unvarying bond lengths

and valence angles. Three approaches have been developed to
take the only remaining factor, substituent electronegativity,
into account:
1. Derive the mathematical dependence of 3J on electronegativity.
2. Empirical allowance by the use of chemical shifts that depend on

electronegativity in a similar fashion as 3J.

3. Eliminate the problem
through
the use of the ratio (the R value) of
CHEM 430
NMR
3
54 or related
two J coupling constants
that respond to the same
Spectroscopy
dihedral angles and that have the same multiplicative dependence

NMR - The
Coupling
Constant

46

VICINAL COUPLINGS

These more sophisticated versions of the Karplus method have

been used quite successfully to obtain reliable quantitative

results.
The existence of factors other than the dihedral angle results in

ranges of vicinal coupling constants at constant even in

structurally analogous systems.
Saturated

hydro-carbon chains (HCC H) exhibit vicinal

couplings in the range 3 9 Hz, depending on substituent
electronegativity and rotamer mixes and 8.90 Hz for . Higher
substituent electronegativity always lowers the vicinal coupling
constant. In small rings, the variation is almost entirely the
result of substituent electronegativity, with cis ranges of 7 13
Hz and trans ranges of 4 10 Hz in cyclopropanes.

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VICINAL COUPLINGS

These more sophisticated versions of the Karplus method have

been used quite successfully to obtain reliable quantitative

results.
The existence of factors other than the dihedral angle results in

ranges of vicinal coupling constants at constant even in

structurally analogous systems.
Saturated

hydro-carbon chains (HCCH) exhibit vicinal

couplings in the range 39 Hz, depending on substituent
electronegativity and rotamer mixes.

Higher substituent electronegativity always lowers the vicinal

coupling constant. In small rings, the variation is almost entirely

the result of substituent electronegativity, with cis ranges of 7
13 Hz and trans ranges of 4 10 Hz in cyclopropanes.
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VICINAL COUPLINGS

In small rings, the variation is almost entirely the result of

substituent electronegativity, with cis ranges of 7 13 Hz and

trans ranges of 4 10 Hz in cyclopropanes.
Coupling constants in oxiranes ( epoxides) are smaller because

of the effect of the electronegative oxygen atom.

J is proportional to the overall bond order, as in benzene and in

naphthalene. The ortho-coupling in benzene derivatives varies
over the relatively small range of 6.7 8.5 Hz, depending on the
resonance and polar effects of the substituents.
3

The presence of heteroatoms in the ring expands the range at

the lower end down to 2 Hz, because of the effects of

electronegativity ( pyridines) and of smaller rings (furans,
pyrroles).
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VICINAL COUPLINGS

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FIRST ORDER SPECTRA

LONG- RANGE COUPLINGS Coupling between protons over more

than three bonds is said to be long range. Sometimes coupling
between 13C and protons over more than one bond also is called
long range, but the term is inappropriate for 2J( CCH) and
3J( CCCH). Long- range cou-pling constants between protons
normally are less than 1 Hz and frequently are unob-servably
small. In at least two structural circumstances, however, such
couplings com-monly become significant. Overlap. Interactions of
bonds with electrons of double and triple bonds and aromatic rings
along the coupling pathway often increase the magnitude of the
coupling constant. One such case is the four bond allylic coupling, ,
with a range of about to and typical values close to . Larger values
are ob-served when the saturated C Ha bond is parallel to the p
orbitals ( 4- 31). This s p + 1 - 3 Hz - 1 Hz HC C CH S P C
H( s) p

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LONG RANGE COUPLINGS

As can be deduced from the reduced J values for vicinal coupling

and the Karplus relationship, the greater the number of

intervening bonds the less opportunity for orbital overlap over
long range (> 3 bond)
Long- range coupling constants between protons normally are

less than 1 Hz and frequently are unobservably small.

In at least two structural circumstances, however, such couplings

commonly become significant.

Allylic and homoallylic coupling
W-coupling
In cases where a rigid structural feature preserves these

overlaps, however, long range couplings are observed

especially where C-H -bonds interact with adjacent -systems
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LONG RANGE COUPLINGS

Allylic systems are the simplest example of a 4J coupling

Here, if the allyl C-Ha bond is orthogonal to the system,4J = 0

Hz; if this bond is parallel to the vinyl C-H a bond, 4J = 3 Hz

In acyclic systems, the dihedral angle is averaged over both

favorable and unfavorable arrangements, so an average

found, as in 2- methylacryloin
Ring

J is

constraints can freeze bonds into the favorable

arrangement, as in indene or in an exactly parallel arrangement
as in allene (right)
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LONG RANGE COUPLINGS

When this type of coupling is extended over five bonds, it is

referred to as homoallylic coupling

Examples include the meta- and para- protons to the observed

proton on an aromatic ring and acetylenic systems:

H

H
C C C C
H
H

J = 0-1

J 1-3

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Spectroscopy

J 0-1 Hz

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LONG RANGE COUPLINGS

Rigid aliphatic ring systems exhibit a specialized case of long

range coupling W-coupling 4JW

The more heavily strained the ring system, the less flexing can

occur, and the ability to transmit spin information is preserved

H
H

H
H

J = 0-1

J =3

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J = 7 Hz

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LONG RANGE COUPLINGS

Although coupling information always is passed via electron-mediated

pathways, in some cases part of the through- bond pathway may be

skipped, and effect known as through-space coupling
Two nuclei that are within van der Waals contact in space can interchange

spin information if at least one of the nuclei possesses lone pair electrons found most commonly, but not exclusively, in H F and F F pairs.
The six- bond H--F coupling is negligible on the left (2.84 ) but is 8.3 Hz on

the right ( 1.44 ) ( the sum of the H and F van der Waals radii is 2.55 ).

This is likely is important in the geminal F C F coupling, which is unusually

large: 2JFCF for sp3 CF2 (~200 Hz, 109.5o) compared to sp2 CF2 (~50 Hz, 120o)

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SPECTRAL ANALYSIS

Analysis of coupling constants in first-order spectra

The general scheme for the interpretation and analysis of 1 st order

multiplets:
Some helpful constraints:
For every signal split into a multiplet, the component J-value(s) must

match some other multiplet in the spectrum

The distance (Hz) between the two outermost peaks in a multiplet is

equal to the sum of each of the coupling constants

The smallest J-value is typically given by the difference between the

first and second peaks in the multiplet

First order multiplets are symmetrically distributed about the center
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SPECTRAL ANALYSIS

Analysis of coupling constants in first-order spectra

Method:
1. Your book suggests letting the spectrometer do the work,
however this method still requires spectral common sense
2. Our method is adapted from:
Hoye, T. R.; Hanson, P. R. Vyvyan, J. R. J. Org. Chem. 1994, 59, 40964103

and basically builds the same tree analysis from the

branches on in
3. This paper is a well loved and regarded classic by 17 years of

grateful graduate students

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SPECTRAL ANALYSIS

Lets start with a simple spectrum:

H

Crotonic acid (trans-2-butenoic acid)

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H3C

O
C OH
H

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SPECTRAL ANALYSIS

Assuming we analyze the spectrum as we have before, we

should get a structure similar (or isomeric) to the actual
one:
O
Simple spectrum:
13
C NMR:
4 unique carbons (too few for aromatic)
1 C=O; 2-alkenyl, 1 alkyl

C OH

H3C

H NMR:
2 multiplets in the alkene region
1 multiplet in the alkyl region
In CDCl3, the acidic proton appears at d 12.4
(acid)
Integrals are 1(a):1:1:3
1

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SPECTRAL ANALYSIS

Without much effort, and any more detailed analysis of chemical

shifts, several possibilities arise:
H
H3C

O
C OH
H

H3C
H

O
C OH
H

CHEM 430 NMR

Spectroscopy

H
H

O
C OH
CH3

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SPECTRAL ANALYSIS

From analysis of J-values and knowledge of which protons are

coupled by the various J-values can finish the analysis:
Inspection of the three multiplets shows the following Hz values:

Ha
2150.34
2143.45
2136.39
2134.75
2129.50
2127.86
2120.97
2114.08

Hb
1767.89
1766.25
1764.61
1762.96
1752.46
1750.82
1749.02
1747.38

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Spectroscopy

Hc
580.98
579.18
573.93
572.29

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SPECTRAL ANALYSIS

Start with the simplest multiplet:

Hc is an apparent doublet of doublets (dd)
Step 1:
The distance between the first two lines always
represents the smallest J value
If the ratio of these two lines (integral) is 1:1, this J is
unique; if it is 1:2, 1:3, etc. there are two or more
identical smallest J s
Label this Jsmall
H
c

580.98 579.18 = 1.80 Hz

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Spectroscopy

580.98
579.18
573.93
572.29

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SPECTRAL ANALYSIS

Step 2: (most difficult step for complex multiplets)

Find the full set of pairs within the multiplet that are
separated by Jsmall
Each pair will have a reflected partner through the
center of the multiplet
For pairs where one of the lines has a relative
intensity >1, that line will be part of more than one
pair
While these two
may not seem
580.98 579.18 = 1.80 Hz
equal, they must
579.18 573.93 = 5.25 Hz
be matched if 1st
573.93 572.29 = 1.64 Hz
order

580.98 579.18 = 1.80 Hz

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Hc
580.98
579.18
573.93
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SPECTRAL ANALYSIS

Step 3:
Find the centers of each of the pairs generated in step
2
These will collectively represent a new pattern (as if
the Jsmall was selectively decoupled)
As with step 1, the spacing between the first two lines
of this multiplet represent the next smallest J
Label this J as med-small, etc. as necessary
580.98

Hc
580.98
579.18
573.93
572.29

580.08

579.18
580.08 - 573.11 = 6.97
573.93

573.11

572.29

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SPECTRAL ANALYSIS

Step 4:
Find the midpoint(s) of this new pair(s), and repeat step 3
Step 5:
Repeat as necessary until all J-values have been found
Remember, it must be internally consistent and all the J values
must add up to the difference between the outer peaks of the
multiplet.
We check:
The two J s we determined are 1.80 (1.64) and 6.97
(1.80+1.64)/2 + 6.97 = 8.69
The difference between the outermost peaks of the multiplet:
580.98 572.29 = 8.69

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SPECTRAL ANALYSIS

This effectively generates the tree-diagram discussed in

the text:

Jmed
= 6.97 Hz
med

This proton is coupled to two

other protons, with coupling
constants of 1.72 and 6.97;
(dd, 6.97, 1.72)

Jsmall
= 1.72 Hz
small

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SPECTRAL ANALYSIS

Repeat the analysis with the next most complex multiplet, look for
possible J-values of 1.72 and 6.97. Analyzing the Hb proton;
apparent doublet of quartets (dq):
Hb
1767.89
1766.25

Step 1&2 Step 3&4

1.64 Hz

1768.71

1.64 Hz

1767.07

1.65 Hz

1765.43

1764.61
1762.96
1752.46
1750.82
1749.02

Step 5

1.64 Hz 1769.53
1765.43
1.64 Hz 1767.89

1.64 Hz

15.51 Hz
1.64 Hz
1.80 Hz
1.64 Hz

symmetrical
Check:

1747.38
CHEM 430 NMR
Spectroscopy

1749.92

1.64 + 1.64 + 1.64 + 15.51 = 20.43

1767.89 1747.38 = 20.51
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SPECTRAL ANALYSIS

The tree diagram for Hb:

Jlarge
= 15.51 Hz
large

Jsmall
= 1.64 Hz
small
Jsmall
= 1.64 Hz
small

We see three
generational iterations of
the 1.64 similar to ~1.7
as found for Hc
We also see a new
constant of 15.51

Jsmall
= 1.64 Hz
small

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SPECTRAL ANALYSIS

Lastly, repeat the process for Ha; looking for 1.64, 15.51 or 6.97:
Analyzing the Ha proton; apparent doublet of quartets (dq):
Ha
2150.34
2143.45
2136.39
1.64 Hz
2134.75
2129.50
1.64 Hz
2127.86
2120.97
2114.08

Step 1&2 Step 3&4

6.89 Hz

2146.91

7.06 Hz

2139.84

6.89 Hz

2132.95

Step 5

7.07 Hz 2143.29
2139.85
6.89 Hz 2136.40

6.89 Hz

15.43 Hz
6.89 Hz
6.89 Hz
6.89 Hz

symmetrical
Check:

CHEM 430 NMR

Spectroscopy

2124.42

6.89 + 6.89 + 6.89 + 15.43 = 36.10

2150.34 2114.08 = 36.26
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SPECTRAL ANALYSIS

The tree diagram for Ha:

Jmed
= 15.43 Hz
med
We see three generational
iterations of the 6.89 similar to
Hc
Jsmall
= 6.89 Hz
small
Jsmall
= 6.89 Hz
small

We also see a new constant of

a similar constant to 15.51, at
15.43

Jsmall
= 6.89 Hz
small

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SPECTRAL ANALYSIS

From analysis of J-values we can finish the analysis:

Ha has
coupling
constants of
15.51 and
6.89

Hb has
coupling
constants of
1.64 and
15.51

Hc has
coupling
constants of
1.72 and 6.97

Conclusion: Ha is coupled to Hb and Hc

Hb is coupled to Ha and Hc
Hc is coupled to Hb and Ha
Wow.
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SPECTRAL ANALYSIS

Conclusion:
On such a small system, the conclusion that all three of these proton
families are coupled to one another is trivial; on more complex systems,
this is a powerful tool to determine the position and relationship of
protons on chains or rings
In this system, it helps us deduce which isomer we are observing by

analysis of the magnitude of the coupling constants that were generated

For each isomer, hypothesize as to what Js would be observed:

H
H3C

O
C OH
H

Jtrans 1Hs = 11-18

Jallyl = 1-3
Jtrans = 15.5

H3C
H

O
C OH

O
C OH

CH3

Jcis 1Hs = 6-15 Hz

Jallyl = 1-3

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Jgeminal 1Hs = 1-3 Hz

No allylic coupling

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SPECTRAL ANALYSIS

Analysis of coupling constants in first-order spectra

Another Method:
1. From our adapted method:
Hoye, T. R.; Hanson, P. R. Vyvyan, J. R. J. Org. Chem. 1994, 59,
4096-4103 There is a second method for determining coupling
constants graphical analysis
2. For first-order spectra, there are a finite number of

combinations of an observed 1H with a maximum number of

interactions
3. Theoretically, the maximum 3J interactions would be nine:
4. In synthetically interesting systems (middle of chains, rings,

etc.) it is typically 2-4 couplings

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SPECTRAL ANALYSIS

Another Method:
5. The authors of the article suggest the method of visual pattern
recognition to save some of the tedium of the more analytical
analysis we just covered
6. In the paper, they generated a series of tables that

systematically cover the most commonly encountered spin

systems
7. For each table, an example compound is used to show where

such a spin pattern would be observed

8. It is suggested that you go through the paper, in conjunction

with your text (as a reference for representative J-values) to

see how each of the tables apply to the example the authors
used
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SPECTRAL ANALYSIS

Example:
In
each table, one coupling
constant is varied (Jz) while all
others are held constant
As a consequence for any table you

see a symmetrical distribution of

the multiplet which converge as Jz
approaches zero at the bottom of
each table
1Hs

that are exemplified are

highlighted by a circle or square

Note, as we have discussed the Js

is equal to the distance between

the outermost peaks in a multiplet
(Hz scale below CHEM
each 430
graphical
NMR
analysis)
Spectroscopy

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SPECTRAL ANALYSIS

Example:
It is important to note, that as
additional coupling decreases, or
certain couplings become equal,
the patterns simplify to what we
recognize from the n+1 rule
Therefore, it should start to be clear

that the n+1 rule is a highly

coincidental case where all possible
couplings (3J s) become equal
In other words, the n+1 rule is the

exception, and the first order

relationships we have just
discussed are the rule
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SECOND ORDER SPECTRA

Second- order spectra are characterized by peak spacings that

do not correspond to coupling constants, by nonbinomial

intensities, by chemical shifts that are not at resonance
midpoints, or by resonance multiplicities that do not follow the n
+ 1 rule
Even when the spectrum has the appearance of being first

order, it may not be.

Lines can coincide in such a way that the spectrum assumes a

simpler appearance than seems consistent with the actual

spectral parameters ( a situation termed deceptive simplicity).

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SECOND ORDER SPECTRA

For example, in the ABX spectrum,

the X nucleus is coupled to two

nuclei ( A and B) that are closely
coupled (AB/J <<<10) .
Under these circumstances, the A

and B spin states are fully mixed,

and X responds as if the nuclei
were equivalent.
Thus the ABX spectrum resembles

an A2X spectrum, as if JAX = JBX .

In the ABX spectra at the right (a)

AB = 3.0 Hz, in (b) AB = 8.0 Hz

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SECOND ORDER SPECTRA

The AA'XX' spectrum often is observed as a deceptively simple

pair of triplets, resembling A2X2.

In this case, it is the A and A' nuclei that are closely coupled ( and

JAA' is large).
Such deceptive simplicity is not eliminated by raising the field

because A and A' are chemically equivalent.

The chemist should beware of the pair of triplets that falsely

suggests magnetic equivalence ( A 2X2) and equal couplings , when

the molecular structure suggests AA'XX'.
Sometimes the couplings between A and X may be observed by

lowering the field to turn the AA'XX' spectrum into AA'BB' with a
larger number of peaks that may permit a complete analysis.
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SECOND ORDER SPECTRA

Another example of second-order complexity occurs in the ABX

spectrum (or, more generally, AxByXz) when A and B are very

closely coupled, JAX is large, and JBX is zero.
With no coupling to B, the X spectrum should be a simple

doublet from coupling to A.

Since A and B are closely coupled, however, the spin states of A

and B are mixed, and the X spectrum is perturbed by the B spins

(the phenomenon has been termed virtual coupling, which is
something of a misnomer, since B is not coupled to X).

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SECOND ORDER SPECTRA

Methyl
resonance at 60
MHz

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SECOND ORDER SPECTRA

Sometimes proton spectra are second order even at 500 MHz or

higher ( aside from the AA' case).

Some institutions still have access only to iron core, 60 MHz

spectrometers, which produce largely second- order proton spectra.

In each case, these spectra may be clarified somewhat by the use of

paramagnetic shift reagents. These molecules contain unpaired spins

and form Lewis acid base complexes with dissolved substrates.

The unpaired spin exerts a strong paramagnetic shielding effect

(downfield) on nuclei close to it. The effect drops off rapidly with
distance, so that those nuclei in the substrate that are closest to the
site of acidbase binding are affected more.

Consequently, the shift to higher frequency varies through the

substrate and hence leads to greater separation of peaks.

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SECOND ORDER SPECTRA

Two

common
shift
reagents
contain
lanthanides:
tris(
dipivalomethanato)
europium(III)

2( tris(dipivalomethanato)europium(III)2( pyridine) [called

Eu(dpm)3 without pyridine] and 1,1,1,2,2,3,3-heptafluoro-7,7dimethyl-octanedionatoeuropium( III) [or Eu( fod)3].

Shift reagents are available with numerous rare earths as well

as other ele-ments -- Almost all organic functional groups that

are Lewis bases have been found to respond to these reagents.
When

the shift CHEM

reagent
is chiral, it can complex with
430 NMR
92
enantiomers and generate
separate resonances
from which
Spectroscopy
enantiomeric ratios may be obtained.

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FIRST ORDER SPECTRA

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FIRST ORDER SPECTRA

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FIRST ORDER SPECTRA

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