Fragmentation
In mass spectrometry, fragmentation is the
dissociation of energetically unstable molecular ions
(M+ion formed by electron bombardment in the ion
chamber) into smaller ions called as fragment ions or
daughter ions. This fragment ion gives information
regarding the structure of the compound.
Importance of Fragmentation
1)Fragmentation of molecule produce large no of ions
with different molecular weight and in mass spectrum
separate peaks will be obtained for each fragment ions.
2) In Mass spectrometry, Molecular ion peak is important
peak to determine molecular weight of compound and
fragment ion peaks also useful to determine molecular
weight and structural information of the unknown
molecule.
3) The frequency and size of fragments are depended on
the structure & bond energy of sample molecule and
unique spectrum will be obtain for particular type of
compound due to unique pattern of fragmentation.
General rules for predicting prominent peaks (Electron
impact ionization method)
1)The existence of molecular ion peak in the spectrum is
dependent on the stability of molecular ion. The order
of decreasing stability of molecular ions is aromatic and
heteroaromatic compounds > conjugated polyenes >
alkenes > cyclo-alkanes > ketones > n-alkanes-ethers >
acids > alcohols > amines. Thus molecular ions are
usually very abundant in compounds contain aromatic
or heteroaromatic ring system.
2) In alkanes, the relative intensity (height) of molecular
ion peak is greatest for straight chain compounds. The
relative intensity of molecular ion peak decreases with
increased degree of branching and also with increasing
molecular weight in homologous series.
3) The fragmentation is favored at more substituted
compound because tertiary carbocation is more stable
than secondary, which is more stable than primary.
4) In alkyl substituted ring compounds,
fragmentation favored at the bond at ß position in
the ring to produce resonance stabilized benzyl ion
5) Saturated rings containing side chain, lose the
side chain at α bond and formation of ring fragment
cation
6) The cleavage of C-X bond is more difficult than that of
C-C bond and if it occurred, the positive charge will be
carried by carbon atom and not by hetero atom (due to
more electron density)
7) Compounds containing a carbonyl group tend to
undergo fragmentation and positive charge remaining
with carbonyl group portion.
8) Stevenson Rule
If two fragment ions compete with each other, the fragment
with the lowest ionization energy will be formed more frequently and
more intense than other.
In this example propenium ion fragment showing more
intense peak due to lowest ionization energy.
Types of Fragmentation
Three types of fragmentation:
1) Homolytic cleavage(α cleavage)
2) Heterolytic cleavage
3)Mclafferty rearrangement
Homolytic cleavage
In homolytic cleavage, a covalent bond breaks and bonding electron
pair is shared between each ion produce in the cleavage.
In homolytic cleavage fragmentation, one radical ion and one
fragment ion (with positive charge) will produce.
In general, radical ion do not detected and not showing m/z value as
well as peak, but fragment ion with positive charge show peak.
2) Heterolytic cleavage
It is mainly occurred in carbon attached with hetero atom as C-X and
during the cleavage both bonding electrons will carry by hetero atom
and carbon get positive charge. C-X C+ + X.
In this cleavage carbon with positive charge will show fragment ion
peak, but heteroatom radical do not detected and not showing peak.
3) Mclafferty rearrangement
It is one type of fragmentation pattern in mass spectrometry and in
which rearrangement Reaction occurs in the compounds containing
n electrons, π electrons and γ hydrogens. It involves cleavage of α and
β bond followed by transfer of γ hydrogen atom to the hetero atom
with lone pair of electrons.
In this rearrangement one neutral molecule (do not show peak) and
one fragment ion(show peak) will produce.
Mechanism
It can be explained with one carbonyl compound with γ hydrogen.
In this rearrangement, γ hydrogen interact with carbonyl group and
carbon – γ hydrogen bond is shifted to oxygen. Then carbonyl bond is
shifted to next carbon atom followed by cleavage of next single bond
and shifted to next carbon atom to form double bond.
Note: It will identify the functional group in the molecule by showing
corresponding m/z value. e.g Aldehyde- m/z=44, Acids-m/z=60,
Amides-m/z=59.