Phosphorus‐Centered and Phosphinidene‐Capped Tungsten Chloride Clusters

Black crystalline powders of W 6 PCl 17 and W 4 (PCl)Cl 10 were obtained after reducing WCl 6 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 W 6 PCl 17 is represented by a phosphorus‐centered hexanuclear tungsten cluster, whose (W 6 PCl 11 )Cl 4 a Cl 4/2 a–a chains form a hexagonal stick packing structure. The structure of W 4 (PCl)Cl 10 is represented by a Jahn–Teller distorted tetranuclear tungsten cluster that is interconnected into a layered [W 4 (μ 4 ‐PCl)Cl 6 i ]Cl 8/2 a–a structure containing a chloro‐phosphinidene ligand. Solid‐state 31 P magic‐angle spinning (MAS) NMR spectra, electronic structures, and magnetic properties are reported.