六氯铱（IV）对酚类的质子耦合电子转移氧化反应
Proton-coupled electron-transfer oxidation of phenols by hexachloroiridate(IV).
作者信息
Song Na, Stanbury David M
机构信息
Department of Chemistry and Biochemistry, Auburn University, Auburn, Alabama 36849, USA.
出版信息
Inorg Chem. 2008 Dec 15;47(24):11458-60. doi: 10.1021/ic8015595.
PMID:19006385
Abstract
One-electron oxidation of phenol, 2,4,6-trimethylphenol, and 2,6-dimethylphenol by IrCl(6) 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.
摘要
在水溶液中，IrCl(6) 对苯酚、2,4,6-三甲基苯酚和 2,6-二甲基苯酚的单电子氧化具有简单的pH依赖性，这表明ArOH的双分子氧化较慢，而ArO(-) 的氧化较快。ArOH氧化时高达3.5的H/D动力学同位素效应支持以水作为质子受体的协同质子耦合电子转移。
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