Proton-coupled electron-transfer oxidation of phenols by hexachloroiridate(IV).
One-electron oxidation of phenol, 2,4,6-trimethylphenol, and 2,6-dimethylphenol by [IrCl(6)](2-) in aqueous solution has a simple pH dependence, indicating slow bimolecular oxidation of ArOH and faster oxidation of ArO(-). H/D kinetic isotope effects as large as 3.5 for oxidation of ArOH support concerted proton-coupled electron transfer with water as the proton acceptor.
Song
Na
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Department of Chemistry and Biochemistry, Auburn University, Auburn, Alabama 36849, USA.
Stanbury
David M
DM
D001557:Benzenesulfonates / Q000737:chemistry; D004579:Electron Transport; D006863:Hydrogen-Ion Concentration; D007495:Iridium / Q000737:chemistry*; D007700:Kinetics; D008956:Models, Chemical; D008958:Models, Molecular; D009603:Nitroso Compounds / Q000737:chemistry; D010084:Oxidation-Reduction; D010636:Phenols / Q000737:chemistry*; D013113:Spin Labels; D013816:Thermodynamics; D014867:Water
D001557:Benzenesulfonates; D009603:Nitroso Compounds; D010636:Phenols; D013113:Spin Labels; D014867:Water; C010978:hexachloroiridic acid; D007495:Iridium; C048757:3,5-dibromo-4-nitrosobenzenesulfonate