Publication
584
J.
Am. Chem. Soc., 126 (49), 16051-16057,
2004
DOI: 10.1021/ja045989u S0002-7863(04)05989-X |
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Fragmentation of Aryl Halide  Anion Radicals. Bending of the Cleaving Bond and Activation vs Driving
Force Relationships
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Cyrille Costentin ,
Marc Robert and Jean-Michel Savéant*
Contribution from the Laboratoire d'Electrochimie Moléculaire, Unité Mixte
de Recherche Université, CNRS No. 7591, Université de Paris 7, Denis Diderot, 2
place Jussieu, 75251 Paris Cedex 05, France
*saveant
@laposte.net
Recent rate data for very fast cleaving of aryl chloride and bromide anion
radicals may be accommodated satisfactorily within rate constant versus
ArX/ArX -
standard potential existing correlations provided the standard potential is
determined experimentally. Cyclic voltammetry is used for this purpose, taking
careful account of the electron transfer/fragmentation reaction mixed character
of the kinetics. The ensuing activation/driving force relationships allow the
determination of the intrinsic barriers, the magnitude of which are discussed in
the framework of a new Morse curve model that includes and emphasizes the role
of bond bending. |
