General route for the synthesis of terminal phosphanylphosphido complexes of Zr(IV) and Hf(IV): Structural investigations of the first zirconium complex with a phosphanylphosphido ligand

Abstract

Reactions of R 2P–P(SiMe 3)Li with [Cp 2MCl 2] (M = Zr, Hf) in hydrocarbons yield the related terminal phosphanylphosphido complexes [Cp 2M(Cl){(Me 3Si)P–PR 2-κ P 1}] (R = i Pr and t Bu). The solid state structures of [Cp 2M(Cl){P(SiMe 3)–P iPr 2-κ P 1}] (M = Zr, Hf) were established by single crystal X-ray diffraction studies. The phosphido-P atoms adopt almost planar geometries and the phosphanyl P atoms adopt pyramidal geometries. The reaction of a mixture of (Me 3Si) 2PLi and Ph 2P–P(SiMe 3)Li with [CpZrCl 3] in toluene yields the dinuclear complex [Cp 2Zr 2Cl 5(Ph 2PPPSiMe 3)(Li THF DME)].