title: Hydridosilylamido complexes of Ta and Mo isolobal with Berry's zirconocenes: syntheses, β-Si-H agostic interactions, catalytic hydrosilylation, and insight into mechanism.
abstract: The syntheses of novel Group 5 and Group 6 hydrosilylamido complexes of the type R(ArN[double bond, length as m-dash])M{N((t)Bu)SiMe2-H}X (M = Ta, R = Cp; M = Mo, R = ArN; X = Cl, H, OBn, Me) are described. The various substituents in the X position seem to play the key role in determining the extent of β-agostic interaction with the Si-H bond. The Mo agostic hydrido complex (ArN[double bond, length as m-dash])2Mo{η(3)-N((t)Bu)SiMe2-H}H is a pre-catalyst for the hydrosilylation of carbonyls. The stoichiometric reaction between benzaldehyde and (ArN[double bond, length as m-dash])2Mo{η(3)-N((t)Bu)SiMe2-H}H gives the benzoxy complex (ArN[double bond, length as m-dash])2Mo{N((t)Bu)SiMe2-H}(OBn), which showed a similar catalytic reactivity compared to the parent hydride. Mechanistic studies suggest that a non-hydride mechanism is operative.
authors.affiliation: Chemistry Department, Brock University, Niagara Region, 1812 Sir Isaac Brock Way, St. Catharines, ON L2S 3A1, Canada. gnikonov@brocku.ca.
authors.forename: Nicolas A
authors.initials: NA
authors.lastname: McLeod
authors.forename: Lyudmila G
authors.initials: LG
authors.lastname: Kuzmina
authors.forename: Ilia
authors.initials: I
authors.lastname: Korobkov
authors.forename: Judith A K
authors.initials: JA
authors.lastname: Howard
authors.forename: Georgii I
authors.initials: GI
authors.lastname: Nikonov