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Article

The Standard Redox Potential of the Phenyl Radical/Anion Couple

Claude P. Andrieux* and Jean Pinson*;

Contribution from the Laboratoire d'Electrochimie Molculaire, Universit Paris 7-Denis Diderot, Unit Mixte Universit Paris 7-CNRS 7591, 2 Place Jussieu, 75251, Paris Cedex 05, France

J. Am. Chem. Soc., 2003, 125 (48), pp 14801–14806

DOI: 10.1021/ja0374574

Publication Date (Web): November 11, 2003

In papers with more than one author, the asterisk indicates the name of the author to whom inquiries about the paper should be addressed.

, andrieux@paris7.jussieu.fr, ; , jean.pinson@laposte.net

Abstract

The voltammogram of aryldiazonium tetrafluoroborates in acetonitrile (ACN), at low concentration, shows a first one-electron wave followed at a more negative potential by a small second wave; this last one corresponds to the reduction of the radical formed at the level of the first wave. Simulation of the voltammogram permits one to determine the standard redox potential of the radical/anion couple E°(Ph^•/Ph^-) = 0.05 V/SCE and the reduction mechanism of the diazonium cation. An electron transfer concerted with the cleavage of the C−N bond furnishes the aryl radical; this radical undergoes two competitive reactions: reduction at the electrode and H-atom transfer.

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