CHEMICAL SHIFTS

 It gives information on the environment of nucleus of interest. The NMR frequency of

a nucleus in a molecule is determined principally by its gyromagnetic ratio γ and the
strength B of the magnetic field it experiences.

𝛾B
=
2𝜋

This means in a 9.4 Tesla field, the 1H and 13

C nuclei resonate at 400 and 100.6 MHz
respectively.

 ν depends on the position of the nucleus in the molecule (environment) or to be more

precise, on the local electron distribution. Chemical shift.
 The field, B, actually experienced by a nucleus in an atom or molecule differs slightly
from the external field B0,
 B is slightly smaller than B0
 The nucleus is thus shielded from the external field by its surrounding electrons. The
field that is actually being experienced by the nucleus is thus,

B = B0 -B'.

B' is proportional to B0 (the stronger the external field, the more it ‘stirs up’ the electrons) and
typically 104 – 105 times smaller. Thus, the field at the nucleus may be written as

B = B0 -B' = B0(1- σ)

where σ, the constant of proportionality between B' and B0, is called the shielding constant.
As a result of nuclear shielding, the resonance condition becomes

𝛾 𝐵0 (1−σ)
=
2𝜋

The resonance frequency of a nucleus is therefore characteristic of its environment.

Measuring Chemical shifts

 It is common practice to define the chemical shift in terms of the difference in

resonance frequencies between the nucleus of interest (ν) and a reference nucleus
(νref), by means of a dimensionless parameter, δ:

1
 (𝝂−𝝂𝒓𝒆𝒇 )
δ =106
𝝂𝒓𝒆𝒇

 The frequency difference ν - νref is divided by νref so that δ is a molecular property

independent of the magnetic field used to measure it.
 The factor of 106 simply scales the numerical value of δ to a more convenient size: δ
values are quoted in parts per million (ppm).
 The reference signal most conveniently obtained by adding a small amount of a
suitable compound to the NMR sample. For 1H and 13
C spectra this is usually
tetramethylsilane (CH3)4Si or TMS.
 Conventionally, NMR spectra are plotted with δ (and ν) increasing from right to left.
Thus more heavily shielded nuclei (larger σ, smaller ν, smaller δ) appear towards the
right-hand side of the spectrum.


δ
Shielding
Frequency

Magnetic field

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Nuclei are said to be shielded or deshielded depending on the presence or absence of electron
density surrounding them.
 For example, the introduction of an electron withdrawing group (e.g., halogen, O,
etc.) will reduce the electron density around a nucleus (deshielding; σ is small) and
the resonance frequency will increase. Conversely, an electron donating substituent
(e.g., CHx, SiHx) will cause increased shielding (σ is large) and lower the resonance
frequency.

Integration

 The area under each NMR absorption peak can be electronically integrated to
determine the relative number of nuclei responsible for each peak.
 The integral of each peak can be provided numerically, and is often accompanied by a
line that represents the integration graphically.
 Intensities of signals can be compared within a particular NMR spectrum only. For
example, 1H intensities cannot be compared to those of 19F or 31P nuclei.
NB: The integration of a peak is a relative number and does not give the absolute
number of nuclei that cause the signal.
i.e. the 1H NMR spectrum of H3C–SiH3 will show two peaks in a 1:1 ratio, as will the
1
H NMR spectrum of (H3C)3C–Si(CH3)3. This is simply because the ratios 3:3 = 9:9 =
1:1.

Spin-spin coupling

 Two protons having significantly different chemical shifts (designated A and X).
Considering chemical shift and integration only, we could represent the spectrum as:

δA δX

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Two spin states:

A X A X

DOUBLET

The splitting, or coupling, is symmetrical about the unperturbed resonances δA and δX, and is
described by the means of a coupling constant, JAX, which has units of Hz.

JAX JAX

δA δX

To review, the influence of the neighbouring spins is called spin-spin coupling and NMR
peaks are split into multiplets as a result. The separation between the two peaks is called the
coupling constant, J, which is expressed in Hz. Spin-spin coupling, has the following
characteristics:
• the magnitude of J measures how strongly the nuclear spins interact with each other.
• coupling is normally a through-bond interaction, and is proportional to the product of
the gyromagnetic ratios of the coupled nuclei. For example, 1JCH = 124 Hz for 1H-13C
coupling in CH4, and 1JSnH = 1931 Hz for 119
Sn-H coupling in SnH4. This happens
because γ(119Sn) is much larger than γ(13C).
• since coupling occurs through chemical bonds, the magnitude of J normally falls off rapidly
as the number of intervening bonds increases. e.g., 1JPH ~700; 2JPH ~20 Hz in

2
JPH
H
H2C P

1 X
JPH H

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Number of bonds separating x
the nuclei JAB Labels describing the two
coupled nuclei

• since spin-spin coupling is a through-bond interaction, it is sensitive to the orientation of the

bonds between two interacting nuclei. This is particularly important for two-bond coupling
constants. The influence of the orientation of the two coupled nuclei can occasionally render
2
J < 3J. For example,

1
J is not affected by the orientation of the coupled nuclei, so it is generally true that
1
J >> 2J or 3J, but it is not always true that 2J > 3J.

• spin-spin interactions are independent of the strength of the applied field. The spacing (in
Hz) between lines at two different field strengths will be the same if it is due to coupling, but
will be proportional to the field strength if it is due to a difference in chemical shift.

Coupling to two equivalent spin ½ nuclei (AX2)

Consider the 1H NMR spectrum of the HF2- anion (i.e., [F--H--F]-). We are observing the 1H
19
nucleus, but it is coupled to two chemically equivalent F (I = 1/2) nuclei. There are four
ways that we can arrange the nuclear spins of the two fluorine nuclei, but only three different
energy states are created, as is explained below:

 The 1H environment where both 19

F spins are “up” is different from that where both
19
F spins are “down”.

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  Arrange things so that one 19F spin is “up” and the other is “down”. The latter case is
degenerate; that is, there is more than one way of accomplishing an “up/down”
arrangement of nuclei, but each “up/down” arrangement has the same energy.
 Begin with a singlet for the 1H nucleus and then couple each 19F nucleus one step at a
time. The coupling of the first 19F nucleus generates a doublet. When each line in this
doublet is split again into a doublet, they overlap identically at the centre of the
signal, generating a single line of intensity two relative to each outer line of intensity
one:

Example 2:

Br

Br

Coupling to three equivalent spin ½ nuclei (AX3)

1
H NMR spectrum of R-CH*-CH3, the nuclear spins of the three equivalent 1H nuclei can be
arranged in four ways to generate a quartet with intensity ratio of 1:3:3:1

3 3 3
JHH JHH JHH

or we can split a singlet into doublets three times to accomplish the same transformation:

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  The intensity pattern is a direct consequence of the number of combinations of the
various nuclear spins that are possible and is described by a series of binomial
coefficients. In practice, it is easiest to determine the intensity pattern by use of a
mnemonic device such as Pascal's triangle.

Coupling to two inequivalent spin ½ nuclei

 AMX spin system, which consists of three nuclei with different chemical shifts and
three distinct coupling constants: JAM, JAX, JMX.
 Predicting the spectrum of A; Four lines are expected because there are four non-
degenerate arrangements of the M and X spins

MX MX MX MX

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 A uncoupled

A coupled to M

A coupled to M and X

Doublet of doublet