Homolyse

In chemistry, homolysis () or homolytic fission is the dissociation of a molecular bond by a process where each of the fragments (an atom or molecule) retains one of the originally bonded electrons. During homolytic fission of a neutral molecule with an even number of electrons, two free radicals will be generated. That is, the two electrons involved in the original bond are distributed between the two fragment species. Bond cleavage is also possible by a process called heterolysis. The energy involved in this process is called bond dissociation energy (BDE). BDE is defined as the "enthalpy (per mole) required to break a given bond of some specific molecular entity by homolysis," symbolized as D. BDE is dependent on the strength of the bond, which is determined by factors relating to the stability of the resulting radical species. Because of the relatively high energy required to break bonds in this manner, homolysis occurs primarily under certain circumstances: Light (i.e. ultraviolet radiation) Heat Certain intramolecular bonds, such as the O–O bond of a peroxide, are weak enough to spontaneously homolytically dissociate with a small amount of heat. High temperatures in the absence of oxygen (pyrolysis) can induce homolytic elimination of carbon compounds. Most bonds homolyse at temperatures above 200°C. Additionally, in some cases pressure can induce the formation of radicals. These conditions excite electrons to the next highest molecular orbital, thus creating a singly occupied molecular orbital (SOMO). Adenosylcobalamin is the cofactor which creates the deoxyadenosyl radical by homolytic cleavage of a cobalt-carbon bond in reactions catalysed by methylmalonyl-CoA mutase, isobutyryl-CoA mutase and related enzymes. This triggers rearrangement reactions in the carbon framework of the substrates on which the enzymes act. Homolytic cleavage is driven by the ability of a molecule to absorb energy from light or heat, and the bond dissociation energy (enthalpy).