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Fragmentation (mass spectrometry)

en.wikipedia.org/wiki/Fragmentation_(mass_spectrometry)

In mass spectrometry, fragmentation is the

dissociation of energetically unstable
molecular ions formed from passing the
molecules in the ionization chamber of a
mass spectrometer. The fragments of a
molecule cause a pattern in the mass
spectrum used to determine structural
information of the molecule.[1]

Toluene Fragmentation

Mass spectrometry techniques

Fragmentation can occur in the ion source (in-source fragmentation) where it is generally not
a desired effect. Ion source conformation is an important criterion in the level of
fragmentation observed.

Desired fragmentation is made in the collision zone (post-source fragmentation) of a tandem

mass spectrometer. It is a part of gas phase ion chemistry and there are different types of
mass fragmentation: collision-induced dissociation (CID), electron-capture dissociation (ECD),
electron-transfer dissociation (ETD), negative electron-transfer dissociation (NETD), electron-
detachment dissociation (EDD), photodissociation, particularly infrared multiphoton
dissociation (IRMPD) and blackbody infrared radiative dissociation (BIRD), surface-induced
dissociation (SID), Higher-energy C-trap dissociation (HCD), charge remote fragmentation.

Fragmentation reactions
Fragmentation is a type of chemical dissociation that can take place by a process of
heterolysis or homolysis.

An example of sigma bond cleavage

Sigma bond cleavage

Sigma bond cleavage is most commonly observed in alkanes. This occurs when an alpha
electron is removed. The C-C bond elongates and weakens causing fragmentation.
Fragmentation at this site produces a charged and a neutral fragment.[2]

An example of radical site-initiated fragmentation

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Radical site-initiated fragmentation

Sigma bond cleavage also occurs on radical cations remote from the site of ionization. The
cation has a radical on a heteratom or an unsaturated functional group. The driving force of
fragmentation is the strong tendency of the radical ion for electron pairing. Cleavage occurs
when the radical and an odd electron from the bonds adjacent to the radical migrate to form
a bond between the alpha carbon and either the heteroatom or the unsaturated functional
group. The sigma bond breaks; hence this cleavage is also known as homolytic bond cleavage
or α-cleavage.[2]

An example of charge site-initiated fragmentation

Charge site-initiated cleavage

The driving force of charge site-initiated fragmentation is the inductive effect of the charge
site in radical cations. The electrons from the bond adjacent to the charged-bearing atom
migrate to that atom, neutralizing the original charge and causing it to move to a different
site. This term is also called inductive cleavage and is an example of heterolytic bond
cleavage.[2]

An example of McLafferty Rearrangement

Rearrangements
Rearrangement reactions are fragmentation reactions that form new bonds producing an
intermediate structure before cleavage. One of the most studied rearrangement reaction is the
McLafferty rearrangement. This occurs to radical cations with unsaturated functional groups.[2]
Other rearrangement reactions include Heterocyclic ring fission (HRF), benzofuran forming
fission (BFF), quinone methide (QM) fission or Retro Diels-Alder (RDA).[3]

See also

References
1. ^ Fred W. McLafferty (1 January 1993). Interpretation of Mass Spectra. University Science
Books. ISBN 978-0-935702-25-5.
2. ^ a b c d Dass, Chhabil (2007). Fundamentals of contemporary mass spectrometry ([Online-
Ausg.]. ed.). Hoboken, NJ [u.a.]: Wiley. ISBN 978-0-471-68229-5.
3. ^ Tandem Mass Spectrometry for Sequencing Proanthocyanidins. Hui-Jing Li and Max L.
Deinzer, Anal. Chem., 2007, volume 79, pages 1739-1748, doi:10.1021/ac061823v

External links
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Fragmentation patterns in the mass spectra of organic compounds

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