title: Fragmentation of aryl halide pi anion radicals. Bending of the cleaving bond and activation vs driving force relationships.
abstract: 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.
authors.affiliation: 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.
authors.forename: Cyrille
authors.initials: C
authors.lastname: Costentin
authors.forename: Marc
authors.initials: M
authors.lastname: Robert
authors.forename: Jean-Michel
authors.initials: JM
authors.lastname: Savéant