Solvent effects on the rates and mechanisms of reaction of phenols with free radicals

DOI	Resolve DOI: https://doi.org/10.1021/ar0682029
Author	Search for: Litwinienko, G.; Search for: Ingold, K. U.¹
Name affiliation	National Research Council of Canada
Format	Text, Article
Journal title	Accounts of Chemical Research
ISSN	0001-4842
Volume	40
Issue	3
Pages	222–230
Subject	free radical; phenol derivative; proton; solvent; water; chemistry; electron transport; hydrogen bond; Electron Transport; Free Radicals; Hydrogen Bonding; Phenols; Protons; Solvents; Water
Abstract	The rates of formal abstraction of phenolic hydrogen atoms by free radicals, Y• + ArOH → YH + ArO•, are profoundly influenced by the hydrogen-bond-accepting and anion-solvation abilities of solvents, by the electron affinities and reactivities (Y-H bond dissociation enthalpies) of radicals, and by the phenol's ring substituents. These apparently simple reactions can occur by at least three different, nonexclusive mechanisms: hydrogen atom transfer, proton-coupled electron transfer, and sequential proton-loss electron transfer. The delicate balance among these mechanisms depends on both the environment and the reactants. The main features of these mechanisms are described, together with some interesting kinetic consequences. © 2007 American Chemical Society.
Publication date	2007
Language	English
Peer reviewed	Yes
NPARC number	21276796
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Record identifier	a200234a-26d4-46e6-a9cf-3555c00efb27
Record created	2015-10-13
Record modified	2020-05-10