The heterolytic cleavage of a molecule according to the general reaction:
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where a-b is an electrofuge and X is a nucleofuge (which may emerge from the reaction in combined form), and the middle group affords the unsaturated fragment c=d. For example,
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The breakdown of a radical into a diamagnetic molecule or ion and a smaller radical, e.g.
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The breakdown of a radical ion in a mass spectrometer or in solution, forming an ion of lower molar mass and a radical, e.g.
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See also: fragmentation reaction (in mass spectrometry)
Source: PAC, 1994, 66, 1077. 'Glossary of terms used in physical organic chemistry (IUPAC Recommendations 1994)' on page 1116 (https://doi.org/10.1351/pac199466051077)