Trivalent Rare-Earth Metal Amide Complexes as Catalysts for the Hydrosilylation of Benzophenone Derivatives with HN(SiHMe2 )2 by Amine-Exchange Reaction.

The rare-earth metal complexes Ln(L1 )[N(SiHMe2 )2 ](thf) (Ln=La, Ce, Y; L1 =N,N''-bis(pentafluorophenyl)diethylenetriamine dianion) were synthesized by treating Ln[N(SiHMe2 )2 ]3 (thf)2 with L1 H2 . The lanthanum and cerium derivatives are active catalysts for the hydrosilylation of benzophenone derivatives with HN(SiHMe2 )2 . An amine-exchange reaction was revealed as a key step of the catalytic cycle, in which Ln-Si-H β-agostic interactions are proposed to promote insertion of the carbonyl moiety into the Si-H bond.