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Oxyradical reactions: from bond‐dissociation energies to reduction potentials
Author(s) -
Koppenol W.H.
Publication year - 1990
Publication title -
febs letters
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.593
H-Index - 257
eISSN - 1873-3468
pISSN - 0014-5793
DOI - 10.1016/0014-5793(90)80239-f
Subject(s) - radical , chemistry , alkoxy group , allylic rearrangement , hydrogen atom abstraction , dissociation (chemistry) , photochemistry , bond dissociation energy , methylene , medicinal chemistry , catalysis , organic chemistry , alkyl
Destructive radical reactions involve alkykl, alkoxyl and alkylperoxyl radicals, as well as alkylhydroperoxides. From bond energies the following reduction potentials vs NHE at neutral pH are derived: Esuo' (RO./ROH) = 1.6 V, E o' (ROO./ROOH) = 1.0 V, E o' (ROOH/RO., H 2 ;0) = 1.9 V, and the two‐electron reduction potential E o' (ROOH/ROH, H 2 O) = 1.7 V. Hydrogen abstraction from a bis ‐allylic methylene group by alkoxyl and alkylperoxyl radicals is favourable with Gibbs energies of −23 and −9, respectively. Similarly, alkoxyl radicals can oxidize alkylhydroperoxides, ΔG o' = −14.