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

Reactions of R2P-P(SiMe3)Li with [Cp2MCl2] (M = Zr, Hf) in hydrocarbons yield the related terminal phosphanylphosphido complexes [Cp2M(Cl){(Me3Si)P-PR2-kappa P-1}] (R = Pr-i and Bu-t). The solid state structures of [Cp2M(Cl)(P(SiMe3)-(PPr2)-Pr-i-kappa 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 (Me3Si)(2)PLi and Ph2P-P(SiMe3)Li with [CpZrCl3] in toluene yields the dinuclear complex [Cp2Zr2Cl5(Ph2PPPSiMe3)(Li THF DME)]. (C) 2011 Elsevier Ltd. All rights reserved.