No abstract

Metathesis reactions between diimido complexes of tungsten(VI) [(ArN)2WCl2] (Ar = 2,6‐iPr2C6H3) and lithium derivatives of diphosphanes R2P–P(SiMe3)Li (R = tBu and iPr) yield two anionic diimido complexes of tungsten with side‐on bonded phosphanylphosphinidene ligands, [(ArN)2WCl(η2‐R2P–P)]–. Both complexes are structurally characterized. A possible reaction mechanism and the role of donor solvents are discussed on the basis of NMR spectroscopic results.

No abstract

No abstract

No abstract

Reactions of (Et(2)N)(2)P-P(SiMe(3))Li with [Cp(2)MCl(2)] (M = Zr, Hf) in toluene or pentane yield the related terminal phosphanylphosphido complexes [Cp(2)M(Cl){η(1)-(Me(3)Si)P-P(NEt(2))(2)}]. The solid state structure of [Cp(2)Hf(Cl){η(1)-(Me(3)Si)P-P(NEt(2))(2)}] was established by single crystal X-ray diffraction. The reaction of (Et(2)N)(2)P-P(SiMe(3))Li with [Cp(2)ZrCl(2)] in THF or DME solutions leads to the formation of deep red crystals of the first neutral diamagnetic zirconocene-phosphanylphosphinidene dimer [Cp(2)Zr{μ(2)-P-P(NEt(2))(2)}(2)ZrCp(2)]. The molecular structure of this compound was confirmed by X-ray diffraction. The reactions of (R(2)N)(2)P-P(SiMe(3))Li with [CpZrCl(3)] yield the related tetraphosphetanes R(2)NP(μ(2)-PSiMe(3))(2)PNR(2), which apparently are formed as a result of a transfer of NR(2) groups from a P atom to the Zr atom.

No abstract

No abstract