Nanosecond Redox Equilibrium Method for Determining Oxidation Potentials in Organic Media

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• 作者：Gonzalo Guirado ; Cavan N. Fleming ; Thor G. Lingenfelter ; Michelle L. Williams ; Han Zuilhof ; and Joseph P. Dinnocenzo
• 刊名：Journal of the American Chemical Society
• 出版年：2004
• 出版时间：November 3, 2004
• 年：2004
• 卷：126
• 期：43
• 页码：14086 - 14094
• 全文大小：236K
• 年卷期：v.126,no.43(November 3, 2004)
• ISSN：1520-5126

文摘

A general, nanosecond equilibrium method is described for determining thermodynamicallymeaningful oxidation potentials in organic media for compounds that form highly reactive cation radicalsupon one-electron oxidation. The method provides oxidation potentials with unusually high precision andaccuracy. Redox ladders have been constructed of appropriate reference compounds in dichloromethaneand in acetonitrile that can be used to set up electron-transfer equilibria with compounds with unknownoxidation potentials. The method has been successfully applied to determining equilibrium oxidationpotentials for a series of aryl-alkylcyclopropanes, whose oxidation potentials were imprecisely knownpreviously. Structure-property trends for oxidation potentials of the cyclopropanes are discussed.