title: Thermodynamic and kinetic control over the reduction mechanism of the Pd(3)(dppm)(3)(CO)(I)(+) cluster.
abstract: The reduction mechanism of the title cluster has been investigated by means of cyclic voltammetry (CV), rotating disk electrode (RDE) voltammetry, and coulometry. The 2-electron reduction proceeds via two routes simultaneously. The first one involves two 1-electron reduction steps, followed by an iodide elimination to form the neutral Pd(3)(dppm)(3)(CO)(0) cluster (EEC mechanism). The second one is a 1-electron reduction process, followed by an iodide elimination, then by a second 1-electron step (ECE mechanism) to generate the same final product. Control over these two competitive mechanisms can be achieved by changing temperature, solvent polarity, iodide concentration, or sweep rate. The reoxidation of the Pd(3)(dppm)(3)(CO)(0) cluster in the presence of iodide proceeds via a pure ECE pathway. The overall results were interpreted with a six-member square scheme, and the cyclic and RDE voltammograms were simulated, in order to extract the reaction rate and equilibrium constants for iodide exchange for all three Pd(3)(dppm)(3)(CO)(I)(n)() (n = +1, 0, -1) adducts.
authors.affiliation: Laboratoire de Synthèse et d'Electrosynthèse Organométalliques, CNRS UMR 5632, Faculté des Sciences Gabriel, Université de Bourgogne, 6 Boulevard Gabriel, 21000 Dijon, France.
authors.forename: Frédéric
authors.initials: F
authors.lastname: Lemaître
authors.forename: David
authors.initials: D
authors.lastname: Brevet
authors.forename: Dominique
authors.initials: D
authors.lastname: Lucas
authors.forename: Alain
authors.initials: A
authors.lastname: Vallat
authors.forename: Yves
authors.initials: Y
authors.lastname: Mugnier
authors.forename: Pierre D
authors.initials: PD
authors.lastname: Harvey