title: Reversible Silylene Insertion Reactions into Si-H and P-H σ-Bonds at Room Temperature.
abstract: Phosphine-stabilized silylenes react with silanes and a phosphine by silylene insertion into E-H σ-bonds (E=Si,P) at room temperature to give the corresponding silanes. Of special interest, the process occurs reversibly at room temperature. These results demonstrate that both the oxidative addition (typical reaction for transient silylenes) and the reductive elimination processes can proceed at the silicon center under mild reaction conditions. DFT calculations provide insight into the importance of the coordination of the silicon center to achieve the reductive elimination step.
authors.affiliation: Université de Toulouse, UPS, and CNRS, LHFA UMR 5069, 188 route de Narbonne, 31062, Toulouse, France.|CSIC-Universidad de Zaragoza, Departamento de Quımica Inorgánica, Instituto de Síntesis Química y Catálisis Homogénea (ISQCH), 50009, Zaragoza, Spain.
authors.forename: Ricardo
authors.initials: R
authors.lastname: Rodriguez
authors.affiliation: Université de Toulouse, UPS, and CNRS, LHFA UMR 5069, 188 route de Narbonne, 31062, Toulouse, France.
authors.forename: Yohan
authors.initials: Y
authors.lastname: Contie
authors.affiliation: Université de Toulouse, UPS, and CNRS, LHFA UMR 5069, 188 route de Narbonne, 31062, Toulouse, France.
authors.forename: Raphael
authors.initials: R
authors.lastname: Nougué
authors.affiliation: Université de Toulouse, UPS, and CNRS, LHFA UMR 5069, 188 route de Narbonne, 31062, Toulouse, France. baceired@chimie.ups-tlse.fr.
authors.forename: Antoine
authors.initials: A
authors.lastname: Baceiredo
authors.affiliation: Université de Toulouse, UPS, and CNRS, ICT FR2599, 31062, Toulouse, France.
authors.forename: Nathalie
authors.initials: N
authors.lastname: Saffon-Merceron
authors.affiliation: UNIV PAU & PAYS ADOUR, Institut des Sciences Analytiques et de Physico-Chimie pour l'Environnement et les Matériaux, IPREM, ECP, UMR 5254, 64053, Pau, France.
authors.forename: Jean-Marc
authors.initials: JM
authors.lastname: Sotiropoulos
authors.affiliation: Université de Toulouse, UPS, and CNRS, LHFA UMR 5069, 188 route de Narbonne, 31062, Toulouse, France. kato@chimie.ups-tlse.fr.
authors.forename: Tsuyoshi
authors.initials: T
authors.lastname: Kato
keywords: X-ray crystallography; density functional calculations; reactive intermediates; silylenes; structure elucidation