Nuclear Magnetic Resonance Spectroscopy

• Nuclear magnetic resonance spectroscopy 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 is used to determine the type and number of H atoms in a
molecule; and
• 13C NMR is used to determine the type of carbon atoms in a
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.

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 Magnetic Fields in NMR
• When a charged particle such as a proton spins on its axis, it creates a
magnetic field, causing the nucleus to act like 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).

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 Energy and Nuclear Spin

• 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 (h) that matches the energy difference
(E) 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.

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 Resonance Energy
• Two variables characterize NMR:
• An applied magnetic field B0, the strength of which is measured in
tesla (T)
• The frequency  of radiation used for resonance, measured in hertz
(Hz), or megahertz (MHz)
• A nucleus is in resonance when it absorbs RF radiation and “spin flips” to
a higher energy state.

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 Resonance Frequency
• The frequency needed for resonance and the applied magnetic field
strength are proportionally related:

• The stronger the magnetic field, the larger the energy difference between
the two nuclear spin states, and the higher the  needed for resonance.
• 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.

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 NMR Schematic
Figure 14.1

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 Electron Environment
• The frequency at which a particular proton absorbs is determined by its
electronic environment.
• Protons in different environments absorb at slightly different frequencies,
so they are distinguishable by NMR.
• 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.
• Only nuclei that contain odd mass numbers (such as 1H, 13C, 19F, and 31P)
or odd atomic numbers (such as 2H and 14N) give rise to NMR signals.

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 1H NMR Spectra
• An NMR spectrum is a plot of the intensity of a peak against its chemical shift,
measured in parts per million (ppm).

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 Interpreting NMR Spectra
• NMR absorptions generally appear as sharp peaks.
• Most protons absorb between 0-10 ppm.
• The terms “upfield” and “downfield” describe the relative location of
peaks.
• Upfield means to the right (higher magnetic field).
• Downfield means to the left (lower magnetic field).
• An external standard, (CH3)4Si (tetremethylsilane) is added to the sample
tube prior to the NMR measurement.
• NMR absorptions are measured relative to the position of a reference
peak at 0 ppm on the  scale due to tetramethylsilane (TMS).
• TMS is a volatile inert compound that gives a single peak upfield from
typical NMR absorptions.

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 Chemical Shift
• 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.

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 Structural Information from Features of a
1H NMR Spectrum

• Number of signals: indicates the number of different types of

hydrogen in a molecule.
• Position of signals: indicates what types of hydrogen the molecule
contains.
• Intensity of signals: indicates the relative amounts (how many) of
each kind of hydrogen in the molecule.
• Spin-spin splitting of signals: gives further information of the
neighboring environment for the various hydrogens in the
molecule.

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 Number of Signals in 1H NMR
• 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.

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 Number of 1H NMR Signals—Examples
Figure 14.2

• To rigorously determine if two hydrogens in a molecule are the same:

• replace each hydrogen by a different atom, Z (e.g., Cl) and
• determine if the resulting compound is the same or different.
• For example, replacement of each methyl hydrogen at
C1 and C5 in pentane produces 1-chloropentane, replacement of each
methylene hydrogen at C2 and C4 leads to 2-chloropentane and at C3
forms 3-chloropentane.

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 Number of 1H NMR Signals—Alkenes
• In comparing two H atoms on a ring or double bond, two protons are
equivalent only if they are cis (or trans) to the same groups.

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 Number of 1H NMR Signals—Cycloalkanes
• To determine equivalent protons in cycloalkanes and alkenes, always
draw all bonds to hydrogen and determine whether or not they are cis
(or trans) to the same groups.

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Enantiotopic Protons

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Diastereotopic Protons

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 Shielding of Nuclei
• In the vicinity of the nucleus, the magnetic field generated by the circulating
electron opposes the applied field and decreases the external magnetic field
that the proton “feels”.
• Since the electron 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.

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 Shielding and Resonant Frequency
• The less shielded the nucleus becomes, the more of the applied magnetic
field (B0) it feels.
• This deshielded nucleus experiences a higher magnetic field strength, so
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.

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