ANALYSIS OF RESULTS IN NUCLEAR MAGNETIC RESONANCE (NMR)

SPECTROSCOPY

Interpreting the NMR Spectrum

NMR interpretation plays a pivotal role in molecular identifications. As interpreting

NMR spectra, the structure of an unknown compound, as well as known structures, can be
assigned by several factors such as chemical shift, spin multiplicity, coupling constants, and
integration. These are the things that we take into account for any resonance on the spectrum
on the purpose of determining the elements in a structure which consists of most organic and
inorganic compound.

Here are the strategies for solving a structure :

1. Molecular formula is determined by chemical analysis such as elementary analysis

2. Double-bond equivalent is calculated by a simple equation to estimate the number of
the multiple bonds and rings. It assumes that oxygen (O) and sulphur (S) are ignored
and halogen (Cl, Br) and nitrogen is replaced by CH. The resulting empirical formula
is CaHb

3. Structure fragmentation is determined by chemical shift, spin multiplicity, integral

(peak area), and coupling constant (1J, 2J).
4. Molecular skeleton is built up using 2-dimensional NMR spectroscopy.
5. Relative configuration is predicted by coupling constant (3J).

The most common NMR spectroscopy is 1H-NMR and 13C-NMR spectra that finds out
structure even though there are other various kinds of NMR spectra such as 14N-NMR, 19F-
NMR, and31P NMR. NMR spectrum shows that x- axis is chemical shift in parts per millon
(ppm). It also contains integral areas, splitting pattern, and coupling constant.
A. CHEMICAL SHIFT

Chemical shift is associated with the Larmor frequency of a nuclear spin to its
chemical environment. Tetramethylsilane [TMS; (CH3)4Si] is generally used for
standard to determine chemical shift of compounds: TMS = 0ppm. In other words,
frequencies for chemicals are measured for a 1H or 13C nucleus of a sample from
the 1H or 13C resonance of TMS. It is important to understand trend of chemical shift
in terms of NMR interpretation. The proton NMR chemical shift is affect by nearness
to electronegative atoms (O, N, halogen.) and unsaturated groups (C=C, C=O,
aromatic). Electronegative groups move to the down field (left; increase in ppm).
Unsaturated groups shift to downfield (left) when affecting nucleus is in the plane of
the unsaturation, but reverse shift takes place in the regions above and below this
plane. 1H chemical shift play a role in identifying many functional groups.

Figure 1 1H chemical shift ranges for organic compound.

The Carbon NMR is used for determining functional groups using characteristic shift
values. 13C chemical shift is affect by electronegative effect and steric effect. If an H atoms in
an alkane is replace by substituent X, electronegative atoms (O, N, halogen), ?-carbon and ?-
carbon shift to downfield (left; increase in ppm) while ?-carbon shifts to upfield. The steric
effect is observed in acyclic and cyclic system, which leads to downshifted chemical shifts.

Figure 2 13C Chemical shift range for organic compound

B. SPIN-SPIN SPLITTING

Spin-spin splitting means that an absorbing peak is split by more than one
neighbour proton. Splitting signals are separated to J Hz, where is called the
coupling constant. The spitting is a very essential part to obtain exact information
about the number of the neighbouring protons. The maximum of distance for splitting
is three bonds. Chemical equivalent protons do not result in spin-spin splitting. When
a proton splits, the protons chemical shift is determined in the centre of the splitting
lines.

Spin Multiplicity (Splitting pattern)

Spin Multiplicity plays a role in determining the number of neighbouring protons.

Here is a multiplicity rules: In case of AmBn system, the multiplicity rule is that
Nuclei of B element produce a splitting the A signal into nB+1 line. The general
formula which applies to all nuclei is 2nI+1, where II is the spin quantum number of
the coupled element. The relative intensities of the each line are given by the
coefficients of the Pascals triangle.
Multinuclear Spectroscopy

There are many types of NMR spectroscopy other than 1H-NMR and 13C-NMR which
are 19F-NMR, 31P-NMR and 14N-NMR.

19F-NMR Spectra for C6F3H2Br

The spectrum below was obtained for a sample of the partially fluorinated aromatic
compound 1-bromo-3,4,5-trifluorobenzene. In this molecule there are two different
chemical environments for the fluorine nuclei, that is the fluorine atoms in the 3 and 5
positions (blue in the diagram) are in one similar environment, while the C-4 fluorine
(para to the bromine) is in its own unique environment. Consider either F-3 or F-5, this
nucleus will couple with the adjacent F-4 nucleus, to give a couplet, and also with the
neighbouring proton, which splits this signal again to generate a doublet of doublets.
The single, unique fluorine, F-4, will couple with the two equivalent fluorine nuclei
(F3 and F5) to give a triplet, and also with the two chemically equivalent protons so
this signal appears as a triplet of triplets.
31P-NMR Spectra for Ph2P (i-C3F7)

The spectra below are for a sample of Ph2P (i-C3F7). In this molecule there are two
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fluorine environments in the ratio 1:6, so the P-NMR spectrum is a doublet of
septets, as shown below.

However these are not completely separated, so there is some overlap in the centre of
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the pattern. The F NMR spectrum has two signals, reflecting the fact that there are
two fluorine environments. The intense peak is due to the six fluorine nuclei of the two
CF3 groups, which couple to the other fluorine, and the phosphorus to give a doublet of
doublets. The weaker signal arises from the unique single fluorine environment, which
shows coupling to the phosphorus and the six fluorine of the CF3 groups, so appears as
a doublet of septets.
 14N-NMR Spectra spectrum of NH4Cl

The 1D 14Nitrogen NMR experiment is much less sensitive than Proton (1H) but has a
much larger chemical shift range. Its signals are broadened by quadrupolar
interactions. The larger the molecule, and the more asymmetric the nitrogen's
environment is, the broader the signal. Hence, the small and highly symmetric
aqueous ammonium ion gives a very sharp line less than one Hertz wide.

Figure 3 Comparison of line-widths of 14N signals. The larger and less symmetric the molecule is, the
wider the signal.
Figure 4 14N spectrum of NH4Cl (1.5 M) in 1M HCl/H2O showing coupling to 1H as a quintet due
to the presence of four protons in an AX4 coupling pattern.