Phosphorus-Centered and Phosphinidene-Capped Tungsten Chloride Clusters


  • Dedicated to Professor John D. Corbett on the occasion of his 85th birthday


Black crystalline powders of W6PCl17 and W4(PCl)Cl10 were obtained after reducing WCl6 with red phosphorus at 370 and 500 °C. The crystal structures were determined by single-crystal and powder X-ray diffraction analyses. The structure of W6PCl17 is represented by a phosphorus-centered hexanuclear tungsten cluster, whose (W6PCl11)Cl4aCl4/2a–a chains form a hexagonal stick packing structure. The structure of W4(PCl)Cl10 is represented by a Jahn–Teller distorted tetranuclear tungsten cluster that is interconnected into a layered [W44-PCl)Cl6i]Cl8/2a–a structure containing a chloro-phosphinidene ligand. Solid-state 31P magic-angle spinning (MAS) NMR spectra, electronic structures, and magnetic properties are reported.