NMR Spectroscopy
Electromagnetic Spectrum
X-ray Ultraviolet - Visible Infrared Microwave
diffractometry Pi and non-bonding Molecular Molecular NMR
nucleus electrons Vibration and rotation Rotation Proton Spin
valence
electrons
Mass Spectrometry
Proton (1H) NMR Spectroscopy
• The number of signals shows how many different kinds of protons are present
• The location of the signals shows how shielded or de shielded the proton is.
• The intensity of the signal shows the number of protons of that type.
• Signal splitting shows the number of protons on adjacent atoms.
NMR Signal generated due to
interaction of Radio waves with
Nuclei
Are all nuclei NMR active ?
Spin active nuclei gives NMR
• In general, nuclei composed of an odd number of protons (1H and its isotopes,
14N 19F, and 31P) or an odd number of neutrons (13 C) show magnetic behavior
(spin active nuclei)
• When an external magnetic field is applied, hydrogen
nuclei can align with the external field or against it.
Phenomena of energy absorption
(Resonance & relaxation phenomena)
Resonance is a phenomenon that occurs when the matching vibrations of
another object increase the amplitude of an object’s oscillations
Radio waves applied which causes the spin to flip and the nuclei
are said to be in resonance with Bo
• As nuclei relax back to the low-energy alignment, energy in the radio wave frequency
is released. This energy is detected and recorded as peaks on a spectrum.
• Free Induction Decay (FID), which is the combined decay of nuclear
spins from various molecules present in the sample after excitation
NUCLEAR SHIELDING AND DESHIELDING
• Electron surrounding the spin active nuclei can also generate their own magnetic
field which is called as induced magnetic field, which oppose the applied magnetic
field in the nucleus region.
The induced magnetic field generated by the e- around the nucleus is not uniform.
Thus each proton in the different electronic environment show slightly
different magnetic field due to the circulation of e- in the neighboring bond.
The external magnetic field is uniform over the entire molecule and therefore cannot
differentiate to the different types of the proton.
However the induced magnetic field generated by the e- around the nucleus is not
uniform, this situation makes the different spin active nuclei 9proton) to be non-
equivalent.
Thus each proton in the different electronic environment show slightly different
magnetic field due to the circulation of e- in the neighboring bond.
For Shielding
For Deshielding
Proton environments
• In a compound, the protons are bonded to other
atoms and so there are more electrons in the
region of the protons.
• These electrons affect the external magnetic field
experienced by the proton.
• The energy gap between high- and low-energy
states will be slightly different.
• The frequency of radiation emitted as the nuclei
relax back to the low-energy state will also be
different.
• Protons emitting radiation of the same frequency
are said to be in the same proton environment.
Determining proton environments
Example: How many proton environments are there in ethanol?
H H The OH proton
is in a third
H C C O environment.
H
The three CH3 H H
protons are in one
environment.
The two CH2
protons are in a
second
environment.
Preparing a sample
• To obtain the 1H NMR spectrum of a sample it is usually necessary to dissolve
the sample in a solvent.
• Solvents must not contain protons that will interfere with the sample being
measured.
• A solvent must:
• contain no hydrogen atoms, eg tetrachloromethane, CCl4
or
• have the hydrogen atoms replaced with deuterium (2H), eg CDCl3 or CD3OD.
Explaining spectra
TMS (tetramethylsilane) is
added to the solvent and
The scale runs from right
provides a reference peak.
to left and is called the
The protons in TMS are
chemical shift. It is
assigned the value
measured in parts per
0 ppm and the rest of the
million (ppm). Peaks to the
spectrum is calibrated
left of TMS peak are said to
relative to this.
be downfield of TMS.
Interpreting low-resolution1H
NMR spectra
Points to note:
• Each peak in a low-resolution spectrum represents one proton environment.
• The type of proton environment can be identified by looking up the chemical
shift in a correlation table (data book).
• The area under the peak relates to the number of protons in the
environment.
Example 1
Methyl ethanoate
H O H
H C O C C H
H H
By comparing the
heights of the
integration curves we
can determine the
The area under the ratio of protons in
peak gives information each environment.
about how many
protons are in each
environment.
In this spectrum the
The area is given as height ratio is 1:1 so
an integration curve there is an equal
and the height of the number of protons
curve can be in each
measured. environment.
Solving problems
• It is helpful to lay out your interpretations in a table.
Peak shift (ppm) Integration height (mm) Ratio
2.1 30 1
3.8 30 1
High resolution
High-resolution spectra are run using a higher radio frequency and the peaks
have more detail.
Compare the spectra below for methyl propanoate.
O
H
H C
C O
C
H H H C H High-resolution NMR for
H methyl propanoate.
H
Low-resolution NMR for
methyl propanoate.
This spectrum is for pentan-3-one. The peaks
show that there are two proton environments.
Can you assign these peaks to the structure?
O
H H
H C H
C
C
H H
C
C CH3
H H
H H
CH2
When the spectrum is expanded it can be seen
that each peak is made up of a number of peaks.
These are called multiplets.
Quartet:
Triplet:
four peaks in
three peaks in
the group.
the group.
Other multiplets include
singlets and doublets.
n + 1 rule
• The number of peaks in a multiplet can give
additional information about the structure.
• The splitting of peaks is caused by the
neighbouring carbon’s hydrogen atoms.
• Protons in the same environment are said to be
equivalent and as such behave as one proton.
• This follows the n + 1 rule.
• n is the number of hydrogen atoms attached to the
next-door carbon
• n + 1 is how many peaks will be seen in the cluster.
CH3CH2COCH2CH3
CH3
CH2 Split by 2
protons on
next-door
Split by 3 carbon, so n = 2,
protons on n + 1 = 3 peaks.
next-door
carbon so n = 3,
n + 1 = 4 peaks.
Example 2 – Assign the peaks and suggest a
structure
Molecular formula C3H7Br
H H H
H C C C Br
H H H CH3
CH2 A triplet due to
A triplet due
CH2 group
to CH2 group
adjacent.
This is not a simple
CH2 adjacent.
quartet. There are
extra splittings due
to CH3 and CH2
neighbouring
groups.
