An Introduction to NMR Spectroscopy

Shelby Feinberg and Steven Zumdahl

Nuclear magnetic resonance spectroscopy (NMR) has risen to the same level of
importance as electronic and vibrational spectroscopy as a tool for studying molecular properties,
particularly structural properties. Although the following discussion of NMR specifically deals
with hydrogen atom nuclei in organic molecules, the principles described here apply to other
types of molecules as well. Many other types of nuclei (
1
!,
1"
#,
1
$, etc.) have nuclear spins and
thus can be studied using NMR techni%ues.
!ertain nuclei, such as the hydrogen nucleus (but not carbon&1' or o(ygen&1)), have a
nuclear spin. *he spinning nucleus generates a small magnetic field termed . +hen placed in a
strong e(ternal magnetic field, called ,o, the nucleus can e(ist in two distinct spin states- a low
energy state A, in which is aligned with the e(ternal magnetic field, ,o, and a high energy state
., in which is opposed to the e(ternal magnetic field, ,o (figure 1). Alignment of with ,o is
the more stable and lower energy state.
Figure 1
/n NMR, transitions from the more stable alignment, A, (with the field) to the less stable
alignment, ., (against the field) occur when the nucleus absorbs electromagnetic energy that is
H
o

H
o

Spin + 1/2
Parallel
A
Low Energy
Spin 1/2
Anti-parallel
B
High Energy
e(actly e%ual to the energy separation between the states (0). *his amount of energy is usually
found in the radiofre%uency range. *he condition for absorption of energy is called the condition
of resonance. /t can be calculated as the following-
1 h ,
2 '
h 3
0 4 = =
h 5 $lanc67s constant
, 5 the strength of the applied magnetic field, ,o, at the nucleus
5 the gyromagnetic ratio (a constant that is characteristic of a particular nucleus)
5 the fre%uency of the electromagnetic energy absorbed that causes the change in
spin states
*here are three features of NMR spectra that we will focus on- the number and si8e of
signals, the chemical shift, and spin&spin coupling.
Number and Size of Signals
9et7s consider how the NMR spectrometer can distinguish between hydrogen nuclei and
produce multiple signals. Magnetically e%uivalent hydrogen nuclei produce one signal. *hese
hydrogen nuclei e(perience the same local environment. #or e(ample, in a molecule such as
diethyl ether (#igure '), there are two sets of magnetically e%uivalent hydrogens. *he hydrogens
labeled a are si( magnetically e%uivalent methyl hydrogens, while the hydrogens labeled b are
four magnetically e%uivalent methylene hydrogens. Notice that the methyl (a) hydrogens are all
located ad:acent to a carbon containing two hydrogen atoms. Additionally, the methylene (b)
hydrogens are all located ad:acent to an o(ygen atom and a carbon atom containing three
hydrogen atoms.
Figure 2
CH
3
CH
2
O CH
2
CH
3
a
b
b
a
.ecause of rapid rotations about sigma bonds and molecular symmetry, the si( methyl hydrogens
(a) and the four methylene hydrogens (b) comprise two individual magnetically e%uivalent
groups of hydrogens. *he methyl hydrogens (a) e(perience a different total magnetic field than
the methylene hydrogens (b), because of different local magnetic fields. As a result, the
resonance energy, 0, corresponding to the fre%uency of absorption, , will be different for these
two groups of hydrogen nuclei. *hus, the NMR spectrometer can distinguish between groups of
hydrogen nuclei which e(perience different local magnetic fields. ;ifferent fre%uencies are
re%uired for the two different groups of hydrogens, thereby producing two distinct signals.
*he areas of the signals are directly proportional to the number of hydrogens. <o, in the
case of diethyl ether, the two pea6s have an area ratio of -' (or )-=), because there are si(
methyl hydrogens (a) and four methylene hydrogens (b). +e will loo6 at an actual spectrum
presently.
The Chemical Shift
+hen an organic molecule is placed in an e(ternal magnetic field, ,o, each hydrogen
nucleus e(periences a total field that is the sum of ,o and two other local magnetic fields- one
produced by bonding and non&bonding electrons, ,e, and the other produced by neighboring
protons which possess a nuclear spin, ,h. *hus, the applied magnetic field (,o) is constant,
while the magnetic fields produced as ,e and ,h are not constant. *he magnetic field produced
by the neighboring electrons (,e) determines the position (relative fre%uency) of an NMR pea6
(called the chemical shift). *he magnetic fields produced by neighboring nuclei (,h) are smaller
than ,e and cause splitting of an NMR pea6 (called spin&spin coupling). *his will be discussed
later.
#or the moment, let7s assume that ,h is 8ero. *here is no spin&spin coupling. >nder
these conditions, the total magnetic field, ,, e(perienced by a particular nucleus is given by ,o ?
,e. *hat is, we are assuming that the resonance energy is only dependent on the sum of the
e(ternal magnetic field and the magnetic field produced by neighboring electrons. A mathe&
matical representation of the value of this resonance energy is the following-
1 h ) , , (
2 '
h 3
0 4 e o = + =
/f we vary the fre%uency () of the electromagnetic energy until h 5 0, absorption will cause a
transition in spin states, and a signal will be recorded by the NMR spectrometer.
*he position of an NMR signal is recorded relative to the position of the signal of an
internal standard. *his standard is commonly tetramethyl silane (*M<), (!,)=<i. /f *M<
absorbs at fre%uency s, and the hydrogen nucleus of interest absorbs at , the spectrometer will
record a signal at
@ 1A
1
) 1 1 (
)
o
s
=

, where o is the spectrometer fre%uency (commonly )A

megacycles per second). is called the position of absorption, or the chemical shift, e(pressed
as parts per million (ppm) on a scale of A&1A ppm. *M< absorbs at A.A ppm, while most nuclei
absorb downfield towards 1A ppm. *he value of is independent of ,o, but it ;B0< depend on
,e. #igure gives a few e(amples of how neighboring atoms affect the chemical shifts of
hydrogen atoms.
Figure 3
RCH
O
RCOH
O
H
C
C
H
C
O
H
C
H
X
C
H

C
H
C
C
C !or O"
C
H
!#at$%"
&'S
1( ) * + , - . 3 2 1 ( !pp/"
0own1iel$ 2p1iel$
Shiel$ing 0e#hiel$ing
H
o

,ydrogen nuclei which absorb at large are said to be deshielded from the e(ternal
magnetic field. *hese signals appear downfield (towards 1A ppm) from *M< because the
fre%uency at which they absorb differs greatly from the fre%uency of the *M< hydrogens. As a
result, the value of s is large. ;eshielding is caused by ad:acent atoms which are strongly
electronegative (e.g. o(ygen, nitrogen, halogen) or groups of atoms which possess &electron
clouds (e.g. !5B, !5!, aromatics).
9et7s now loo6 at the NMR spectrum of ben8yl acetate (#igure =).
Figure 4
A
)AA AA
c
b
a
*M<
Note that there are three absorptions corresponding to the three sets of magnetically e%uivalent
hydrogens. !ompare the chemical shifts with those given in #igure . *he relative area of the
pea6s corresponds to the number of hydrogens in each set (-'-C).
Spin-Spin Coupling
+e have discussed how the position of the NMR absorption is affected by the magnetic
field produced by neighboring electrons (,e). Now, let7s e(amine how the magnetic field
produced by neighboring protons (,h) affects the splitting of the NMR absorption. *he pea6s
CH
2
O C CH
3
O
a b
c
can appear as singlets, doublets, triplets, etcD 9et7s first consider the absorption of a hydrogen
atom (,() with only one neighboring hydrogen atom (,y) (#igure C).
Figure 5
C
3H
4
C
H
y
3H
4
5
H
o
H
y
5 5 A 5 H
o
+ H
e
+ H
h
!low energy"
H
y
5 5 B 5 H
o
+ H
e
+ H
h
!high energy"
n/r #pe6tr7/ 1or 3H
4
5 inten#ity ratio 5 181
/f we assume that ,( is aligned with ,o, then the neighboring hydrogen nucleus will have
appro(imately e%ual probability of e(isting in either the low energy state, A, or the high energy
state, .. Refer to #igure 1 for a clear picture of these energy states. #or those molecules in
which the neighboring hydrogen nucleus e(ists in the low energy state, its magnetic field (,h)
will add to the magnetic field (,o ? ,e) and for those molecules in which the neighboring
hydrogen nucleus e(ists in the high energy state, its magnetic field (,h) will subtract from the
magnetic field (,o ? ,e). As a result, two different pea6s are observed. A higher fre%uency is
re%uired for the low energy state, while a lower fre%uency is re%uired for the high energy state.
*his two line pattern is called a doublet, and we say that the neighboring hydrogen nucleus (,y)
splits the absorption of ,( into a doublet. *he intensity of the two lines will be e%ual, because
the probability of the neighboring hydrogen nucleus (,y) e(isting in either spin state A or . is
appro(imately e%ual.
+hen there are two magnetically e%uivalent ad:acent hydrogen nuclei, three possibilities
e(ist for their combined magnetic fields (#igure )).
Figure 6
C
3H
4
C
H
y
H
y
3H
4
5
H
o
n/r #pe6tr7/ 1or 3H
4
5 inten#ity ratio 5 18281
H
y
5 !low energy"
H
y
5 !/i$$le energy"
H
y
5 !/i$$le energy"
H
y
5 !high energy"
Note that both can have spin state A, one can have spin state A and the other have spin state ., or
both can have spin state .. *hese three possibilities have a probability ratio of 1-'-1, which
correspond to three different absorption fre%uencies. *he appearance of the resulting NMR
signal is a three line pattern, called a triplet, with intensities 1-'-1.
+hen there are three magnetically e%uivalent neighboring hydrogen nuclei (#igure E), the
absorption splits into a %uartet with intensity pattern 1---1 for similar reasons to those
aforementioned.
Figure 7
C
3H
4
C
H
y
H
y
3H
4
5
H
o
n/r #pe6tr7/ 1or 3H
4
5 inten#ity ratio 5 1838381
H
y
5 !9ery low energy"
H
y
5 !/e$% low energy"
H
y
5 !/e$% high energy"
H
y
5 !9ery high energy"
H
y
/n general, N magnetically e%uivalent neighboring hydrogen nuclei will split the
absorption into N ? 1 lines. *he intensity ratios are e%ual to the coefficients of the e(pansion (a
+ b)
N
, or pascal7s triangle.
*he spacing between the lines of a doublet, triplet, or %uartet is dependent on the
coupling constant. /t is given the symbol F, and it is measured in units of cycles per second.
!oupling constants range in magnitude from A to 'A cps. Bbservable coupling will generally
occur between hydrogen nuclei which are separated by no more than three sigma bonds. #or
e(ample, in the molecule '&butanone (#igure G), hydrogens from groups a and b split one
another because they are only separated by three bonds. ,owever, hydrogens from group c are
not split by any other hydrogens because they are separated from other hydrogens by more than
three sigma bonds.
Figure 8
*M<
A
)AA AA
0(amples of typical coupling constants are given in #igure ".
CH
3
CH
2
CCH
3
O
a b c
Figure 9
C
H
H
C C
H
H
H C O H
C C
H H
C C
H
H
H C C
O
H
12-1- 6p# 13-1* 6p# ( 6p#
,-* 6p# (-3 6p# 1-3 6p#
+-12 6p# ,-) 6p# C C
H H
H
H
Note that coupling is never observed between magnetically e%uivalent hydrogen atoms.
9et7s now consider the coupling of hydro(ylic protons (B,). ,ydro(ylic protons do not
split other protons, nor are they split by other protons. *hese protons undergo e(change between
two molecules of alcohol. *his e(change is so fast that these protons sample molecules with all
possible spin states, giving rise to a singlet in the NMR spectrum at a position which is the
average for all the spin states of the other hydrogens.
#or e(ample, ethanol gives an NMR spectrum consisting of a triplet, %uartet, and a
singlet, as seen in the ideali8ed spectrum in #igure 1A. 0ven though the hydro(ylic proton is
separated from a methylene hydrogen by three bonds, the signal given by the hydro(ylic proton
is not split by the methylene protons, nor are the methylene hydrogens split by the hydro(ylic
proton because of proton e(change.
Figure 10
CH
3
CH
2
OH
Now that you7ve learned some of the main principles necessary to e(amine NMR spectra,
try to draw an ideali8ed spectrum for each of the structures given below.
H
3
C C C CH
3
O CH
3
CH
3
C O CH
2
O
CH
2
CH
3
H
3
C C CH
2
O
CH
2
C CH
3
O

COCH
2
CH
3
O
CH
3
CH
3
CH
3
CH
3
CH
2
OC
O
HO C CH
2
C CH
2
C OH
CH
3
CH
3
O
CH
2
CH
3
CH
3
CH
2
CH
2
CH
3
H
3
C CH
2
H
2
tert-:7tyl-a6etate
n-propyl a6etate
a6etonyla6etone
$iethyl 2;.;,-tri/ethyl-3;--pyri$ine$i6ar:o4ylate
3;3-$i/ethylgl7tari6 a6i$
1;3;--triethyl:en<ene
ethyla/ine
1% -
2%
,%
3%
.%
+%
H
3
C
O