Syntheses and structures of the first terminal phosphanylphosphido complex of hafnium [Cp2Hf(Cl){η1-(Me3Si)P- P(NEt2)2}] and the first zirconocene- phosphanylphosphinidene dimer [Cp_2Zr{μ_2-P-P(NEt _2)_2}_2ZrCp_2]

摘要

Reactions of (Et_2N)_2P-P(SiMe_3)Li with [Cp_2MCl_2] (M = Zr, Hf) in toluene or pentane yield the related terminal phosphanylphosphido complexes [Cp_2M(Cl) {η_1-(Me_3Si)P-P(NEt_2)_2}]. The solid state structure of [Cp_2Hf(Cl){η~1-(Me _3Si)P-P(NEt_2)_2}] was established by single crystal X-ray diffraction. The reaction of (Et_2N)_2P- P(SiMe_3)Li with [Cp_2ZrCl_2] in THF or DME solutions leads to the formation of deep red crystals of the first neutral diamagnetic zirconocene-phosphanylphosphinidene dimer [Cp_2Zr{μ _2-P-P(NEt_2)_2}_2ZrCp_2]. The molecular structure of this compound was confirmed by X-ray diffraction. The reactions of (R_2N)_2P-P(SiMe_3)Li with [CpZrCl_3] yield the related tetraphosphetanes R_2NP(μ _2-PSiMe_3)_2PNR_2, which apparently are formed as a result of a transfer of NR_2 groups from a P atom to the Zr atom.