title: Barium-mediated cross-dehydrocoupling of hydrosilanes with amines: a theoretical and experimental approach.
abstract: Alkaline-earth (most prominently barium) complexes of the type [Ae{N(SiMe3 )2 }2 ⋅(THF)x ] and [{N^N}Ae{N(SiMe3 )2 }⋅(THF)x ] are very active and productive precatalysts (TON=396, TOF up to 3600 h(-1) ; Ca<Sr<Ba) for NH/HSi cross-dehydrocoupling, with excellent chemoselectivity in the reaction of (di)amines with (di)hydrosilanes. Experimental and DFT investigations revealed that the reactions proceed by nucleophilic attack of a metal amide at the incoming silane and subsequent turnover-limiting hydrogen transfer to the metal center.
authors.affiliation: Organometallics: Materials and Catalysis Centre, Institut des Sciences Chimiques de Rennes, UMR 6226 CNRS, Université de Rennes 1, Campus de Beaulieu, 263 avenue du Général Leclerc, 35042 Rennes Cedex (France).
authors.forename: Clément
authors.initials: C
authors.lastname: Bellini
authors.affiliation: Organometallics: Materials and Catalysis Centre, Institut des Sciences Chimiques de Rennes, UMR 6226 CNRS, Université de Rennes 1, Campus de Beaulieu, 263 avenue du Général Leclerc, 35042 Rennes Cedex (France). jean-francois.carpentier@univ-rennes1.fr.
authors.forename: Jean-François
authors.initials: JF
authors.lastname: Carpentier
authors.affiliation: University of St Andrews, School of Chemistry, Purdie Building, North Haugh, St Andrews KY16 9ST (UK). st40@st-andrews.ac.uk.
authors.forename: Sven
authors.initials: S
authors.lastname: Tobisch
authors.affiliation: Organometallics: Materials and Catalysis Centre, Institut des Sciences Chimiques de Rennes, UMR 6226 CNRS, Université de Rennes 1, Campus de Beaulieu, 263 avenue du Général Leclerc, 35042 Rennes Cedex (France). yann.sarazin@univ-rennes1.fr.
authors.forename: Yann
authors.initials: Y
authors.lastname: Sarazin
keywords: alkaline earth metals; amines; barium; density functional calculations; reaction mechanisms