Abstract
AbstractBlack 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 [W4(μ4‐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.
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