NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY

Nuclear Magnetic Resonance spectroscopy; abbreviated as NMR is a technique that relies on the
interaction of Radiofrequency (Rf/NMR waves) of EMR with nuclei of molecules placed in a
magnetic field. This technique exploits the magnetic properties of certain atomic nuclei.

Analysis of these nuclei together with other supplementing techniques can be used in determining
structures of compounds which have them or in determining the content or purity of a sample.
For example, NMR can quantitatively analyze mixtures containing known compounds.
Nuclear magnetic resonance (NMR) is a physical phenomenon in which nuclei in a magnetic field
absorb and re-emit electromagnetic radiation.
NMR is also routinely used in advanced medical imaging techniques, such as in
Magnetic Resonance Imaging (MRI).

WORKING PRINCIPLES OF NMR

The NMR spectroscopic experiments are carried out in an NMR Spectrophotometer/ Spectrometer.
The Experiments involves using energy in the form of electromagnetic radiation (EMR) to pump the
excess alpha () oriented nuclei into the beta () state.

When the energy is removed, the energized nuclei relaxes back to the  state and gives signals typical
if the nuclei present.
The sample to be analysed is put in solution form into the NMR machine, an air jet spins the sample
tube to give a more uniform sample to scan.

Solvents used should be deuterated.

This means that there are deuterium atoms in the place of the hydrogens of the solvent molecule.

WHICH NUCLEI ARE NMR ACTIVE?

In practice it is 1H, 13C, 19F, and 31P that are most often observed by NMR spectroscopy due to the
best -orientation of their nuclei.
Tetramethylsilane (TMS) is usually used as the reference compound at zero-point resonance
frequencybecause of the following reasons:
1. TMS protons are highly shielded: silicon is slightly less electronegative than carbon, and
therefore donates some additional shielding electron density.
2. This gives its protons the lowest frequency than most other signals because its methyl protons
are in a more electron dense environment than most protons
3. It is easily be removed from the sample by evaporation due to its volatile properties:
Its being volatile is convenient for recovery of samples analyzed by NMR spectroscopy
4. Because all twelve hydrogen atoms in a TMS molecule are equivalent, its 1H NMR spectrum
consists of a singlet at  = 0 ppm.
 5. Very few organic molecules contain protons with chemical shifts that are negative relative to
TMS

Structure of Tetramethylsilane and its NMR spectrum (C4H12Si)

CHEMICAL SHIFT
It is a measure of how far the signal produced from the proton of a sample/compound under
investigation is from the reference compound/TMS signal, and it usually measured using the (delta)
scale.
The TMS/reference compound is at the zero position (0) on the very right of the spectrum, and as it
moves toward the left, the ppm values become larger.

Ppm stands for parts per million, and it is the unit used to measure chemical shift.
The proton chemical shifts range from 0 -15 ppm.

The chemical shift is more/less identical for a specific proton regardless of the spectrometer used.
The formula for the chemical shift is:

(delta () = Distance downfield from TMS (Hz) = parts per million (ppm)
Operation frequency of the spectrometer (MHz)

PROTON NUCLEAR MAGNETIC RESONANCE (1H NMR)

1
H NMR analysis of a sample targets all hydrogen-1 nuclei in a compound.
The data obtained can be used to determine the structure of the unknown compound.
The sample is dissolved in a deuterated (2H) solvent to eliminate signals of the protons of the solvent.

S/No. Solvent Deuterated Solvent Operating frequency (MHz)

1. CH3OH CD3OD 300 - 600
2. CH2Cl2 CD2Cl2 500 - 600
3. CHCl3 CDCl3 300 - 600
4. (CH3)2SO (CD3)2SO/DMSO-d6 400 - 600
5. H2O D2O
6. CCl4 May also be used

N/B: Operating frequencies depend on the polarity of the sample being analysed
NMR spectra are recorded in solution and solvent protons must not be allowed to interfere, hence
they are deuterated. Deuterated solvents (deuterium 2H denoted s D) are therefore used to dissolve
the sample. 1H NMR scale runs from 0 – 14 ppm where 0 ppm side is considered as high field while
14 ppm is considered as down field.

The chemical shift of a particular type of a proton is the position on the -scale (in ppm) relative to
TMS position at 0
Typical  /Ppm Values for Protons in Different Chemical Environments are shown in the
Table below.
Integrals and Integration
 The peaks on NMR Spectrum not only distinguishes the different types of protons present
in a test molecule, but also the total number
 The area under the peak is proportional to the number of protons that the peak represents
 The integration measures the area under the peak of a particular signal
 The integration gives the relative ratio of the number of H for each peak

Coupling
 The proximity of other "n" H atoms on neighbouring carbon atoms causes the signals to be
split into "n+1" lines.
 This is also known as the multiplicity or splitting of each signal yielding doublets, triplets, and
quartet.
 Type a protons have 2 neighbours giving a multiplicity of [2 +1 = 3] hence the triplet.
 Type b protons have 3 neighbours giving a multiplicity of [3 +1 = 4] hence the quartet.


N/B:
1. The chemical environment around a particular H causes changes in the chemical shift and
2. The more electronegative neighbours causes more shift
DIAMAGNETIC SHIELDING AND DISHIELDING

Consider methane (CH4)

All the protons of CH4 are said to be chemically equivalent, thus will give a singlet signal at  0.23
ppm, but with an integration for 4 protons

Compare the signal for protons of methane with the signals of the halogenated derivatives

The presence of the halogens causes a chemical shift for methane protons as shown above. F causes
more shift downfield from  0.23 (CH4) to  4.26 (CH3F)
Non-equivalent protons show different chemical shifts due to the difference in their immediate
electronic environment.
CH4 has a big electron cloud/density that shields the full magnetic force (B0): local diamagnetic
shielding, giving a reduced effective magnetic force (Beff), thus resulting in a much lower resonance
frequency ( 0.23 ppm).
For CH3F, the highly electronegative F pulls the electron cloud towards itself hence lowering the
electron density/cloud. This is referred to as deshielding effect/less diamagnetic shielding. The
overall exposure to B0 is high giving a stronger Beff hence a higher resonance frequency of  4.26
ppm. As electronegativity increases, so is the dishielding effect hence higher chemical shift.
The deshielding effect of an electronegative substituent diminishes with distance as shown below:

1
H NMR Spectrum of Ethane

EXERCISE 2
Explain the differential resonance frequency observed in the following compounds;