The unusual reaction of semiquinone radicals with molecular oxygen

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Journal titleJournal of Organic Chemistry
Pages18301841; # of pages: 12
SubjectOxidation; pH effects; Photolysis; Rate constants; Stoichiometry; Hydroquinones; Peroxyl radicals; Semiquinone radicals; Molecular oxygen; acetonitrile; chlorobenzene; oxygen; radical; semiquinone; styrene; addition reaction; article; autooxidation; chemical reaction; chemical reaction kinetics; chemical structure; photolysis; Kinetics; Oxidation-Reduction; Oxygen; Quinones; Thermodynamics
Abstract(Chemical Equation Presented) Hydroquinones (benzene-1,4-diols) are naturally occurring chain-breaking antioxidants, whose reactions with peroxyl radicals yield 1,4-semiquinone radicals. Unlike the 1,2-semiquinone radicals derived from catechols (benzene-1,2-diols), the 1,4-semiquinone radicals do not always trap another peroxyl radical, and instead the stoichiometric factor of hydroquinones varies widely between 0 and 2 as a function of ring-substitution and reaction conditions. This variable antioxidant behavior has been attributed to the competing reaction of the 1,4-semiquinone radical with molecular oxygen. Herein we report the results of experiments and theoretical calculations focused on understanding this key reaction. Our experiments, which include detailed kinetic and mechanistic investigations by laser flash photolysis and inhibited autoxidation studies, and our theoretical calculations, which include detailed studies of the reactions of both 1,4-semiquinones and 1,2-semiquinones with O2, provide many important insights. They show that the reaction of O2 with 2,5-di-tert-butyl-1,4-semiquinone radical (used as model compound) has a rate constant of 2.4 ± 0.9 × 105 M -1 s-1 in acetonitrile and as high as 2.0 ± 0.9 × 106 M-1 s-1 in chlorobenzene, i.e., similar to that previously reported in water at pH ∼7. These results, considered alongside our theoretical calculations, suggest that the reaction occurs by an unusual hydrogen atom abstraction mechanism, taking place in a two-step process consisting first of addition of O2 to the semiquinone radical and second an intramolecular H-atom transfer concerted with elimination of hydroperoxyl to yield the quinone. This reaction appears to be much more facile for 1,4-semiquinones than for their 1,2-isomers. © 2008 American Chemical Society.
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AffiliationNational Research Council Canada; National Institute for Nanotechnology; NRC Steacie Institute for Molecular Sciences
Peer reviewedYes
NPARC number21276697
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Record identifierf8365be7-d77f-4ff2-b4d8-1232e8f7f7ef
Record created2015-10-13
Record modified2016-05-09
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