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 acc...

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Bibliographic Details
Published in:Journal of the American Chemical Society 2004-11, Vol.126 (43), p.14086-14094
Main Authors: Guirado, Gonzalo, Fleming, Cavan N, Lingenfelter, Thor G, Williams, Michelle L, Zuilhof, Han, Dinnocenzo, Joseph P
Format: Article
Language:English
Subjects:
3-electron s(n)2 reactions
arylcyclopropane cation radicals
carbon bond-cleavage
Chemistry
electrochemistry
electron-transfer reactions
Exact sciences and technology
General and physical chemistry
intrinsic barrier
ohmic drop
photochemistry
Solution properties
Solutions
solvent purification
ultrafast cyclic voltammetry
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Description
Summary: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.
ISSN:0002-7863
1520-5126
DOI:10.1021/ja046946g