Reactions of (Et2N)2P-P(SiMe3)Li with [Cp2MCl2] (M= Zr, Hf) in toluene or pentane yield the related terminal phosphanylphosphido complexes [Cp2M(Cl){η1-(Me3Si)P-P(NEt2)2}]. The solid statestructure of [Cp2Hf(Cl){η1-(Me3Si)P-P(NEt2)2}] was established by single crystal X-ray diffraction. The reaction of (Et2N)2P-P(SiMe3)Li with [Cp2ZrCl2] in THF or DME solutions leads to the formationof deep red crystals of the first neutral diamagnetic...

Reactions of R2P-P(SiMe3)Li with [Cp2MCl2] (M = Zr, Hf) in hydrocarbons yield the related terminal phosphanylphosphidocomplexes [Cp2M(Cl){(Me3Si)P-PR2-jP1}] (R = iPr and tBu). The solid state structures of [Cp2M(Cl){P(SiMe3)-PiPr2-jP1}] (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...

The reaction of R2P–P(SiMe3)Li (R = tBu, iPr) with the diimido molybdenum complex [(ArN)2MoCl2·dme] (Ar = 2,6-iPr2C6H3; dme = 1,2-dimethoxyethane) yielded the side-oncoordinated phosphanylphosphinidene anionic complexes [(2,6-iPr2C6H3N)2Mo(Cl)(η2-P=PR2)]– (7Mo, 8Mo). The thermal decomposition of [(2,6-iPr2C6H3N)2M(Cl)(η2-P=PR2)]–[M = Mo (7Mo), W (8W)] to [(2,6-iPr2C6H3N)2M(Cl)(1,2-η-tBu2P=P–PtBu2)] [M = Mo (3Mo), W (3W)] was investigated...