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-κP1}] (R = iPr and tBu). The solid state structures of [Cp2M(Cl){P(SiMe3)–PiPr2-κP1}] (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)2PLi and Ph2P–P(SiMe3)Li with [CpZrCl3] in toluene yields the dinuclear complex [Cp2Zr2Cl5(Ph2PPPSiMe3)(Li THF DME)].

A new entrance to phosphanylphosphido complexes [Cp2M(Cl){(Me3Si)P–PR2-κP1}] (R = iPr and tBu) was presented. The solid state structures of [Cp2M(Cl){(Me3Si)P–PiPr2-κP1}] (M = Zr, Hf) were established by single crystal X-ray diffraction studies.Figure optionsDownload as PowerPoint slideResearch highlights
► Reactions of Cp2MCl2 (M = Zr, Hf) with R2P–P(SiMe3)Li yield phosphanylphosphido complexes.
► X-ray structures of these complexes reveal almost planar geometry around phosphido-P atoms.
► The Ph2P–P–PSiMe3 ligand was formed in a reaction of [CpZrCl3] with (Me3Si)2PLi and Ph2P–P(SiMe3)Li.