title: Nonclassical β-hydrogen elimination of hydrosilazido zirconium compounds via direct hydrogen transfer.
abstract: Salt metathesis reactions of Cp(2)(NR(2))ZrX (X = Cl, I, OTf) and lithium hydrosilazides ultimately afford hydride products Cp(2)(NR(2))ZrH that suggest unusual β-hydrogen elimination processes. A likely intermediate in one of these reactions, Cp(2)Zr[N(SiHMe(2))t-Bu][N(SiHMe(2))(2)], is isolated under controlled synthetic conditions. Addition of alkali metal salts to this zirconium hydrosilazide compound produces the corresponding zirconium hydride. However as conditions are varied, a number of other pathways are also accessible, including C-H/Si-H dehydrocoupling, γ-abstraction of a CH, and β-abstraction of a SiH. Our observations suggest that the conversion of (hydrosilazido)zirconocene to zirconium hydride and silanimine does not follow the classical four-center mechanism for β-elimination.
authors.affiliation: Department of Chemistry, Iowa State University, Ames, 50011, United States.
authors.forename: KaKing
authors.initials: K
authors.lastname: Yan
authors.forename: Arkady
authors.initials: A
authors.lastname: Ellern
authors.forename: Aaron D
authors.initials: AD
authors.lastname: Sadow