title: Unexpected reaction of the unsaturated cluster host and catalyst [Pd3(mu3-CO)(dppm)3]2+ with the hydroxide ion: spectroscopic and kinetic evidence of an inner-sphere mechanism.
abstract: The title cluster, [Pd(3)(mu(3)-CO)(dppm)(3)](2+) (dppm=bis(diphenylphosphino)methane), reacts with one equivalent of hydroxide anions (OH(-)), from tetrabutylammonium hydroxide (Bu(4)NOH), to give the paramagnetic [Pd(3)(mu(3)-CO)(dppm)(3)](+) species. Reaction with another equivalent of OH(-) leads to the zero-valent compound [Pd(3)(mu(3)-CO)(dppm)(3)](0). From electron paramagnetic resonance analysis of the reaction medium using the spin-trap agent 5,5-dimethyl-1-pyrroline-N-oxide (DMPO), the 2-tetrahydrofuryl or methyl radicals, deriving from the tetrahydrofuran (THF) or dimethyl sulfoxide (DMSO) solvent, respectively, were detected. For both [Pd(3)(mu(3)-CO)(dppm)(3)](2+) and [Pd(3)(mu(3)-CO)(dppm)(3)](+), the mechanism involves, in a first equilibrated step, the formation of a hydroxide adduct, [Pd(3)(mu(3)-CO)(dppm)(3)(OH)]((n-1)+) (n=1, 2), which reacts irreversibly with the solvent. The kinetics were resolved by means of stopped-flow experiments and are consistent with the proposed mechanism. In the presence of an excess of Bu(4)NOH, an electrocatalytic process was observed with modest turnover numbers (7-8). The hydroxide adducts [Pd(3)(mu(3)-CO)(dppm)(3)(OH)]((n-1)+) (n=1, 2), which bear important similarities to the well-known corresponding halide adducts [Pd(3)(mu(3)-CO)(dppm)(3)(mu(3)-X)](n) (X=Cl, Br, I), have been studied by using density functional theory (DFT). Although the optimised geometry for the cluster in its +2 and 0 oxidation states (i.e., cation and anion clusters, respectively) is the anticipated mu(3)-OH form, the paramagnetic species, [Pd(3)(mu(3)-CO)(dppm)(3)(OH)](0), shows a mu(2)-OH form; this suggests an important difference in electronic structure between these three species.
authors.affiliation: Université de Bourgogne, Laboratoire de Synthèse et Electrosynthèse Organométalliques, CNRS UMR 5188, Faculté des Sciences Mirande, 9 Avenue Alain Savary, 21000 Dijon, France.
authors.forename: Cyril
authors.initials: C
authors.lastname: Cugnet
authors.forename: Dominique
authors.initials: D
authors.lastname: Lucas
authors.forename: Frédéric
authors.initials: F
authors.lastname: Lemaître
authors.forename: Edmond
authors.initials: E
authors.lastname: Collange
authors.forename: Armand
authors.initials: A
authors.lastname: Soldera
authors.forename: Yves
authors.initials: Y
authors.lastname: Mugnier
authors.forename: Pierre D
authors.initials: PD
authors.lastname: Harvey