Nanosecond redox equilibrium method for determining oxidation potentials in organic media.
A general, nanosecond equilibrium method is described for determining thermodynamically meaningful oxidation potentials in organic media for compounds that form highly reactive cation radicals upon one-electron oxidation. The method provides oxidation potentials with unusually high precision and accuracy. Redox ladders have been constructed of appropriate reference compounds in dichloromethane and in acetonitrile that can be used to set up electron-transfer equilibria with compounds with unknown oxidation potentials. The method has been successfully applied to determining equilibrium oxidation potentials for a series of aryl-alkylcyclopropanes, whose oxidation potentials were imprecisely known previously. Structure-property trends for oxidation potentials of the cyclopropanes are discussed.
Guirado
Gonzalo
G
Department of Chemistry and the Center for Photoinduced Charge Transfer, University of Rochester, Rochester, New York 14627-0216, USA.
Fleming
Cavan N
CN
Lingenfelter
Thor G
TG
Williams
Michelle L
ML
Zuilhof
Han
H
Dinnocenzo
Joseph P
JP