Nuclear Magnetic Resonance Spectroscopy

Principle & Applications

Nuclear Magnetic Resonance (NMR) Spectroscopy

From here… To here!

 What Kind of States?

electronic UV-Vis

vibrational infrared
microwave
rotational
radiofrequency
nuclear spin

NMR is concerned with change in the direction of spin

orientation as the result of the absorption of
radiofrequency radiation
 Introduction to NMR Spectroscopy
NMR is a powerful analytical technique used to characterize
organic molecules by identifying carbon-hydrogen frameworks
within molecules

Two common types of NMR spectroscopy are used to

characterize organic structure:
• 1H NMR: Determine the type and number of H atoms in a
molecule
• 13C NMR: Determine the type of carbon atoms in the molecule

The source of energy in NMR is radio waves which have long

wavelengths, and thus low energy and frequency

When low-energy radio waves interact with a molecule, they can

change the nuclear spins of some elements, including 1H and 13C
 Nuclear Spin

• The spinning charged nucleus generates a

magnetic field.
• Magnetic nuclei are in resonance with external magnetic field if they absorb
energy and “spin-flip” from low energy state (parallel orientation) to high
energy state (antiparallel orientation).
atomic nuclei in absence of atomic nuclei in presence
magnetic field of external magnetic field

atomic nuclei can either align parallel

(lower E) or antiparallel (higher E) 7
 External Magnetic Field

• When placed in an external field, spinning protons act like

bar magnets.
 Dependence of the difference in energy between lower and
higher nuclear spin levels of the hydrogen atom

Nuclei in different environments (i.e. with different amounts of electron

density around them) will require different amounts of energy to “flip” to
higher energy different spin state
 Two Energy States

• The magnetic fields of the

spinning nuclei will align
either with the external
field, or against the field

• A photon with the right

amount of energy can be
absorbed and cause the
spinning proton to flip.
 The two nuclei that are most useful to
organic chemists are:
• 1H and 13C
• both have spin = ±1/2
• 1H is 99% at natural abundance
• 13C is 1.1% at natural abundance
• Only nuclei that contain odd mass numbers
(such as 1H, 13C, 19F and 31P) give rise to NMR
signals.
1) Even/Even. Nuclei containing even numbers of both protons and neutrons
have I = 0 and therefore cannot undergo NMR. Examples include 4He,12C,16O
and 32S.
2) Odd/Odd. Nuclei with odd numbers of both protons and neutrons have spin
quantum numbers that are positive integers. Examples include14N (I=1),2H
(deuterium, I=1), and10B (I=3).
3) All others. The remaining nuclei (odd/even and even/odd) all have spins that
are half integral. Examples include 1H (I=½), 17O (I=5/2), 19F (I=½), 23Na (I=3/2),
and 31P (I=½).
Every element in the periodic table has at least one isotope that can experience
NMR when placed in a magnetic field. For odd-numbered elements this is the
isotope with highest natural abundance. For even-numbered elements, the
principal isotope will nearly always have I=0, but there will be one or more less
abundant isotopes that are NMR-active.

For example, the most common naturally occurring isotope of carbon (¹²C)
contains 6 protons and 6 neutrons. According to Rule #1 above, ¹²C has I = 0 and
cannot undergo NMR. However, carbon's ¹³C isotope (natural abundance 1.07%)
contains one extra neutron, resulting in a net spin (I =½) and permitting its use in
NMR.
The distribution of
nuclear spins is +
random in the
absence of an
external magnetic
field. +

+
+
• When a charged particle such as a proton spins on its axis, it
creates a magnetic field. Thus, the nucleus can be considered
to be a tiny bar magnet.
• Normally, these tiny bar magnets are randomly oriented in
space. However, in the presence of a magnetic field B0, they
are oriented with or against this applied field. More nuclei are
oriented with the applied field because this arrangement is
lower in energy.
• The energy difference between these two states is very small
(<0.1 cal).
An external magnetic
field causes nuclear
magnetic moments to +
align parallel and
antiparallel to applied
field.
+

+
H0

+
+
There is a slight
excess of nuclear
magnetic moments
+
aligned parallel to
the applied field.
+

+
H0

+
+
Thus, two variables characterize NMR:
• an applied magnetic field B0, the strength of which is
measured in tesla (T), and
• the frequency ν of radiation used for resonance,
measured in hertz (Hz), or megahertz (MHz)—(1 MHz =
106 Hz).
• In a magnetic field, there are now two energy states for
a proton: a lower energy state with the nucleus aligned
in the same direction as B0, and a higher energy state in
which the nucleus aligned against B0

• When an external energy source (hν) that matches the

energy difference (ΔE) between these two states is
applied, energy is absorbed, causing the nucleus to
“spin flip” from one orientation to another

• The energy difference between these two nuclear spin

states corresponds to the low frequency RF region of
the electromagnetic spectrum.
• The frequency needed for resonance and the applied
magnetic field strength are proportionally related:

• NMR spectrometers are referred to as 300 MHz

instruments, 500 MHz instruments, and so forth,
depending on the frequency of the RF radiation used for
resonance.
• These spectrometers use very powerful magnets to
create a small but measurable energy difference
between two possible spin states.
 Some important relationships in NMR

• The frequency of absorbed electromagnetic

radiation for a particular nucleus (such as 1H or
13
C) depends on the molecular environment of
the nucleus (the electronic environment).
• This is why NMR is such a useful tool
for structure determination. The signals of
different protons and carbon atoms in a
molecule show different signals, just like
different functional groups show different
signals in the IR.
Schematic of a NMR Spectrometer
Fig. 13-4, p. 444
 1
H NMR—The Spectrum

• An NMR spectrum is a plot of the intensity of a peak

against its chemical shift, measured in parts per million
(ppm).
 1
H NMR—The Spectrum
•NMR absorptions generally appear as sharp peaks
•Increasing chemical shift is plotted from left to right
•Most protons absorb between 0-10 ppm
•The terms “upfield” and “downfield” describe the
relative location of peaks. Upfield means to the
right. Downfield means to the left
•NMR absorptions are measured relative to the
position of a reference peak at 0 ppm on the δ scale
due to tetramethylsilane (TMS). TMS is a volatile
inert compound that gives a single peak upfield
from typical NMR absorptions.
 Chemical Shift

• Measured in parts per million

• Ratio of shift downfield from TMS (Hz) to total

spectrometer frequency (Hz)

• Same value for 60, 100, or 300 MHz machine

• Called the delta scale.

Delta Scale

Chapter 13 26
 Tetramethylsilane

• TMS is added to the sample

• Since silicon is less electronegative than carbon,

TMS protons are highly shielded. Signal defined
as zero

• Organic protons absorb downfield (to the left)

of the TMS signal
• The chemical shift of the x axis gives the position of an NMR
signal, measured in ppm, according to the following equation:

• By reporting the NMR absorption as a fraction of the NMR

operating frequency, we get units, ppm, that are independent
of the spectrometer
• Four different features of a 1H NMR spectrum provide
information about a compound’s structure:
a. Number of signals
b. Position of signals
c. Intensity of signals
d. Spin-spin splitting of signals
 De-shielding, Less Shielding, More Shielding
• Protons in different environments absorb at slightly
different frequencies, so they are distinguishable by NMR

• The frequency at which a particular proton absorbs is

determined by its electronic environment

• The size of the magnetic field generated by the electrons

around a proton determines where it absorbs

• Modern NMR spectrometers use a constant magnetic

field strength B0, and then a narrow range of frequencies
is applied to achieve the resonance of all protons
Shielding and De-shielding effects
 Shielded Nuclei: Less Shielded or More Shielded
• In the vicinity of the nucleus, the magnetic field generated by the
circulating electron decreases the external magnetic field that the
proton “feels”

• Since the nucleus experiences a lower magnetic field strength, it

needs a lower frequency to achieve resonance. Lower frequency is
to the right in an NMR spectrum, toward a lower chemical shift, so
shielding shifts the absorption upfield
 Shielded Nuclei: Less Shielded or More Shielded

• Depending on their chemical environment, protons in a

molecule are shielded by different amounts
The NMR Spectrum showing less shielded and
more shielded protons
 De-shielded Nuclei

• Deshielded nucleus experiences a higher magnetic field

strength, to it needs a higher frequency to achieve
resonance
• Higher frequency is to the left in an NMR spectrum,
toward higher chemical shift—so deshielding shifts an
absorption downfield

• Protons near electronegative atoms are deshielded, so

they absorb downfield
 1
H NMR—Position of Signals
• In a magnetic field, the six π electrons in benzene circulate
around the ring creating a ring current.
• The magnetic field induced by these moving electrons reinforces
the applied magnetic field in the vicinity of the protons.
• The protons thus feel a stronger magnetic field and a higher
frequency is needed for resonance. Thus they are deshielded and
absorb downfield.
Anisotropic induced magnetic field effects are the result of a local induced magnetic
field experienced by a nucleus resulting from circulating electrons that can either be
paramagnetic when it is parallel to the applied field or diamagnetic when it is opposed to
it.
 1
H NMR—Position of Signals
• In a magnetic field, the loosely held π electrons of the
double bond create a magnetic field that reinforces the
applied field in the vicinity of the protons.
• The protons now feel a stronger magnetic field, and
require a higher frequency for resonance. Thus the
protons are deshielded and the absorption is downfield.
Aldehyde Proton, δ9-δ10

Electronegative
oxygen atom
Shielding and De-shielding effects
▪ How chemical shift is affected by electron density
around a nucleus?
 1
(a) H NMR—Number of Signals
• The number of NMR signals equals the number of
different types of protons in a compound

• Protons in different environments give different NMR

signals

• Equivalent protons give the same NMR signal

 1
(a) H NMR—Number of Signals
• The number of 1H NMR signals of some representative
organic compounds
•cis (or trans) to the same groups.
 (b) 1H NMR—Position of Signals
(as a consequence of shielding & Deshielding)
 1
H NMR—Chemical Shift Values
• Protons in a given environment absorb in a predictable region in
an NMR spectrum
Position of Signals – Role of Electronegativity

• More electronegative atoms

deshield more and give
larger shift values.
• Effect decreases with
distance.
• Additional electronegative
atoms cause increase in
chemical shift.
Position of signals – Role of electron cloud
 NMR Spectral Values
1
H NMR—Chemical Shift Values Regions in the1H NMR
spectrum
 (c) 1H NMR—Intensity of Signals
• The area under an NMR signal is proportional to the number of
absorbing protons

• An NMR spectrometer automatically integrates the area under

the peaks, and prints out a stepped curve (integral) on the
spectrum

• The height of each step is proportional to the area under the

peak, which in turn is proportional to the number of absorbing
protons

• Modern NMR spectrometers automatically calculate and plot the

value of each integral in arbitrary units

• The ratio of integrals to one another gives the ratio of absorbing

protons in a spectrum. Note that this gives a ratio, and not the
absolute number, of absorbing protons.
1
H NMR—Intensity of Signals
 1
H NMR—Spin-Spin Splitting

• Consider the spectrum below:

• Spin-spin splitting occurs only between non-equivalent
protons on the same carbon or adjacent carbons.
Let us consider how the doublet due to the CH2 group on
BrCH2CHBr2 occurs:
• When placed in an applied magnetic field, (B0), the
adjacent proton (CHBr2) can be aligned with (↑) or
against (↓) B0.
• Thus, the absorbing CH2 protons feel two slightly
different magnetic fields—one slightly larger than B0,
and one slightly smaller than B0.
• Since the absorbing protons feel two different
magnetic fields, they absorb at two different
frequencies in the NMR spectrum, thus splitting a
single absorption into a doublet.
The frequency difference, measured in Hz between two
peaks of the doublet is called the coupling constant, J
Let us now consider how a triplet arises:

• When placed in an applied magnetic field (B0), the

adjacent protons Ha and Hb can each be aligned with (↑)
or against (↓) B0.
• Thus, the absorbing proton feels three slightly different
magnetic fields—one slightly larger than B0, one
slightly smaller than B0, and one the same strength as
B0.
 1
H NMR—Spin-Spin Splitting

• Because the absorbing proton feels three different magnetic

fields, it absorbs at three different frequencies in the NMR
spectrum, thus splitting a single absorption into a triplet.
• Because there are two different ways to align one proton with
B0, and one proton against B0—that is, ↑a↓b and ↓a↑b—the
middle peak of the triplet is twice as intense as the two outer
peaks, making the ratio of the areas under the three peaks
1:2:1.
• Two adjacent protons split an NMR signal into a triplet.
• When two protons split each other, they are said to be
coupled.
• The spacing between peaks in a split NMR signal, measured
by the J value, is equal for coupled protons.
Generation of a Triplet
Three general rules describe the splitting patterns commonly seen
in the 1H NMR spectra of organic compounds.

1. Equivalent protons do not split each other’s signals.

2. A set of “n” non-equivalent protons splits the signal of a
nearby proton into (n + 1) peaks.
3. Splitting is observed for non-equivalent protons on the same
carbon or adjacent carbons.

If Ha and Hb are not equivalent, splitting is observed when:

 The (N + 1) Rule
If a signal is split by N equivalent protons,
it is split into N + 1 peaks.
4. Splitting is not generally observed between protons
separated by more than three σ bonds.
The 1H NMR spectrum of 2-bromopropane,(CH3)2CHBr
The 1H NMR spectrum of Ethanol
•Under usual conditions, an OH proton does not split the
NMR signal of adjacent protons.
•The signal due to an OH proton is not split by adjacent
protons.
13.7: Spin-spin splitting in 1H NMR spectroscopy
protons on adjacent carbons will interact and “split” each others
resonances into multiple peaks (multiplets)
n + 1 rule: equivalent protons that have n equivalent protons
on the adjacent carbon will be “split” into n + 1 peaks.

δ= 2.0
3H
δ= 1.2
3H
δ= 4.1
2H

Resonances always split each other. The resonance at δ= 4.1

splits the resonance at δ = 1.2; therefore, the resonance at
δ = 1.2 must split the resonance at δ = 4.2.
65
The multiplicity is defined by the number of peaks and the pattern
(see Table 13.2 for common multiplicities patterns and relative
intensities)

δ= 2.0
s, 3H
δ= 1.2
t, 3H
δ= 4.1
q, 2H

1:2:1

1:3:3:1 66
The resonance of a proton with n equivalent protons on the adjacent
carbon will be “split” into n + 1 peaks with a coupling constant J.
Coupling constant: distance between peaks of a split pattern; J is
expressed in Hz. Protons coupled to each other have the same
coupling constant J.

δ= 2.0
s, 3H
δ= 1.2
t, J=7.2 Hz, 3H
δ= 4.1
q, J=7.2 Hz, 2H

67
•Ethanol (CH3CH2OH) has three different types of protons, so there
are three signals in its NMR spectrum

•The Ha signal is split by the two Hb protons into three peaks (a

triplet)

•The Hb signal is split only by the three Ha protons into four peaks, a
quartet. The adjacent OH proton does not split the signal due to Hb

•Hc is a singlet because OH protons are not split by adjacent

protons.

•Protons on electronegative atoms rapidly exchange between

molecules in the presence of trace amounts of acid or base. Thus,
the CH2 group of ethanol never “feels” the presence of the OH
proton, because the OH proton is rapidly moving from one
molecule to another

•This phenomenon usually occurs with NH and OH protons.

Now consider the spectrum of 1-bromopropane. Since Ha and Hc
are not equivalent to each other, we cannot merely add them
together and use the (n + 1) rule.

The 1H NMR spectrum of 1-bromopropane, CH3CH2CH2Br

 1
H NMR—Protons on Benzene Rings
•Benzene has six equivalent deshielded protons and exhibits a
single peak in its 1H NMR spectrum at 7.27 ppm.
•Monosubstituted benzenes contain five deshielded protons that
are no longer equivalent, and the appearance of these signals is
highly variable, depending on the identity of Z.

The 6.5–8 ppm region of the 1H NMR spectrum of three benzene

derivatives
1
H NMR—Structure Determination
1
H NMR—Structure Determination
1
H NMR—Structure Determination
1
H NMR—Structure Determination
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