title: Intermolecular and intramolecular, platinum-catalyzed, acceptorless dehydrogenative coupling of hydrosilanes with aryl and aliphatic methyl C-H bonds.
abstract: Intermolecular acceptorless dehydrogenative coupling of silanes with arene C-H bonds and intramolecular coupling of silanes with aryl and alkyl C-H bonds occur in good yield in the presence of 5 mol % of TpMe2PtMe2H (TpMe2 = hydridotris(3,5-dimethylpyrazolyl)borate) and related platinum(IV) complexes. The intermolecular reactions of arenes occurred with both trialkyl and dialkylaryl silanes. Intramolecular reactions of dialkylsilylalkylarenes occurred at aryl C-H bonds, and reactions of tributylsilane or dibutylphenylsilane occurred intramolecularly at the aliphatic, primary C-H bond. The reactions of arenes occurred preferentially at the least sterically hindered C-H bonds and preferentially with more electron-poor arenes. Crossover experiments and the lack of reactivity of the arylsilanes with H2 imply that the dehydrogenative silylation of arenes can be irreversible, even in a closed reaction vessel.
authors.affiliation: Department of Chemistry, Yale University, P.O. Box 208107, New Haven, Connecticut 06520-8107, USA.
authors.forename: Naofumi
authors.initials: N
authors.lastname: Tsukada
authors.forename: John F
authors.initials: JF
authors.lastname: Hartwig