Bond cleavage

Bond cleavage, or scission, is the splitting of chemical bonds. This can be generally referred to as dissociation when a molecule
is cleaved into two or more fragments.[1]

In general, there are two classifications for bond cleavage: homolytic and heterolytic, depending on the nature of the process. The
triplet and singlet excitation energies of a sigma bond can be used to determine if a bond will follow the homolytic or heterolytic
pathway.[2] A metal−metal sigma bond is an exception because the bond's excitation energy is extremely high, thus cannot be
used for observation purposes.[2]

In some cases, bond cleavage requires catalysts. Due to the high bond-dissociation energy of C−H bond, around 100 kcal/mol
(420 kJ/mol), a large amount of energy is required to cleave the hydrogen atom from the carbon and bond a different atom to the
carbon.[3]

Contents
Homolytic cleavage
Heterolytic cleavage
Ring-opening
Applications
References

Homolytic cleavage
In homolytic cleavage, or homolysis, the two electrons in a cleaved covalent
bond are divided equally between the products. This process is also known as
homolytic fission or radical fission. The bond-dissociation energy of a bond is Homolytic cleavage
the amount of energy required to cleave the bond homolytically. This enthalpy
change is one measure of bond strength.

The triplet excitation energy of a sigma bond is the energy required for homolytic dissociation, but the actual excitation energy
may be higher than the bond dissociation energy due to the repulsion between electrons in the triplet state.[2]

Heterolytic cleavage
In heterolytic cleavage, or heterolysis, the bond breaks in such a fashion that the
originally-shared pair of electrons remain with one of the fragments. Thus, a
fragment gains an electron, having both bonding electrons, while the other
fragment loses an electron.[4] This process is also known as ionic fission.
Heterolytic cleavage
The singlet excitation energy of a sigma bond is the energy required for
heterolytic dissociation, but the actual singlet excitation energy may be lower
than the bond dissociation energy of heterolysis as a result of the Coulombic attraction between the two ion fragments.[2] The
singlet excitation energy of a silicon–silicon sigma bond is lower than the carbon–carbon sigma bond, even though their bond
strengths are 80kJ/mol and 70kJ/mol respectively, because silicon has higher electron affinity and lower ionization potential than
carbon.[2]

Heterolysis occurs naturally in reactions that involve electron donor ligands and transition metals which have empty orbitals.[4]

Ring-opening
In a ring-opening, the cleaved molecule remains as a single unit.[5] The bond
breaks, but the two fragments remain attached by other parts of the structure. For
example, an epoxide ring can be opened by heterolytic cleavage of one of the
polar carbon–oxygen bonds to give a single acyclic structure.[5]
Epoxide opening

Applications
In biochemistry, the process of breaking down large molecules by splitting their internal bonds is catabolism. Enzymes which
catalyse bond cleavage are known as lyases, unless they operate by hydrolysis or oxidoreduction, in which case they are known
as hydrolases and oxidoreductases respectively.

In proteomics, cleaving agents are used in proteome analysis where proteins are cleaved into smaller peptide fragments.[6]
Examples of cleaving agents used are cyanogen bromide, pepsin, and trypsin.[6]

References
1. Muller, P. (1 January 1994). "Glossary of terms used in physical organic chemistry (IUPAC Recommendations
1994)". Pure and Applied Chemistry. 66 (5). doi:10.1351/pac199466051077 (https://doi.org/10.1351%2Fpac1994
66051077).
2. Michl, Josef (May 1990). "Relationship of bonding to electronic spectra". Accounts of Chemical Research. 23 (5):
127–128. doi:10.1021/ar00173a001 (https://doi.org/10.1021%2Far00173a001).
3. Wencel-Delord, Joanna; Colobert, Françoise (2017). "Super-reactive catalyst for bond cleavage" (https://www.nat
ure.com/articles/d41586-017-07270-0). Nature. pp. 447–448. Bibcode:2017Natur.551..447. (http://adsabs.harvar
d.edu/abs/2017Natur.551..447.). doi:10.1038/d41586-017-07270-0 (https://doi.org/10.1038%2Fd41586-017-0727
0-0). Retrieved 23 February 2018.
4. Armentrout, P.B.; Simons, Jack (1992). "Understanding heterolytic bond cleavage". Journal of the American
Chemical Society. 114: 8627–8633.
5. Parker, R. E.; Isaacs, N. S. (1 August 1959). "Mechanisms Of Epoxide Reactions". Chemical Reviews. 59 (4):
737–799. doi:10.1021/cr50028a006 (https://doi.org/10.1021%2Fcr50028a006).
6. Mander, Lew; Liu, Hung-Wen (2010). Comprehensive Natural Products II: Chemistry and Biology (https://books.g
oogle.co.th/books?id=pkzx2TeYYT8C&pg=RA8-PA462&lpg=RA8-PA462&dq=chemical+cleaving+agents&source
=bl&ots=LHuT09Lyse&sig=aHE4OLnVlIT-19H-WIR_7bjY8pY&hl=en&sa=X&ved=0ahUKEwjyxvr7ibvZAhXKGZQ
KHXudAiwQ6AEIXTAJ#v=onepage&q=chemical%20cleaving%20agents&f=false) (1 ed.). Elsevier. pp. 462–463.
ISBN 978-0-08-045381-1. Retrieved 23 February 2018.

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