title: Water (in water) as an intrinsically efficient proton acceptor in concerted proton electron transfers.
abstract: The oxidation of PhOH in water by photochemically generated Ru(III)(bpy)(3) is taken as prototypal example disclosing the special character of water, in the solvent water, as proton acceptor in concerted proton-electron transfer reactions. The variation of the rate constant with temperature and driving force, as well as the variation of the H/D kinetic isotope effect with temperature, allowed the determination of the reaction mechanism characterized by three intrinsic parameters, the reorganization energy, a pre-exponential factor measuring the vibronic coupling of electronic states at equilibrium distance, and a distance-sensitivity parameter. Analysis of these characteristics and comparison with a standard base, hydrogen phosphate, revealed that electron transfer is concerted with a Grotthus-type proton translocation, leading to a charge delocalized over a cluster involving several water molecules. A mechanism is thus uncovered that may help in understanding how protons could be transported along water chains over large distances in concert with electron transfer in biological systems.
authors.affiliation: Laboratoire d'Electrochimie Moléculaire, Unité Mixte de Recherche Université - CNRS No 7591, Université Paris Diderot, Bâtiment Lavoisier, 15 rue Jean de Baïf, 75205 Paris Cedex 13, France.
authors.forename: Julien
authors.initials: J
authors.lastname: Bonin
authors.forename: Cyrille
authors.initials: C
authors.lastname: Costentin
authors.forename: Cyril
authors.initials: C
authors.lastname: Louault
authors.forename: Marc
authors.initials: M
authors.lastname: Robert
authors.forename: Jean-Michel
authors.initials: JM
authors.lastname: Savéant
mesh_terms: D015082:2,2'-Dipyridyl / Q000031:analogs & derivatives* / Q000737:chemistry; D056831:Coordination Complexes; D004583:Electrons; D010084:Oxidation-Reduction; D019800:Phenol / Q000737:chemistry*; D011522:Protons; D014867:Water / Q000737:chemistry*; D017975:Ruthenium Compounds
chemical_list: D015082:2,2'-Dipyridyl; D056831:Coordination Complexes; D019800:Phenol; D011522:Protons; D014867:Water; C547232:tris(2,2-bipyridine)-ruthenium(II); D017975:Ruthenium Compounds