Phosphorus‐Centered and Phosphinidene‐Capped Tungsten Chloride Clusters

Abstract

Keywords: Tungsten / Cluster compounds / Solid-state structures / X-ray diffraction 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 struc-

Low-temperature preparation of tungsten halide clusters: Crystal structure of the adduct W5Br12 · SbBr3

“…The two slightly distinct [(W 5 ) ] u n i t s i n the structure of I alternate along the one dimensional chain direction (Fig. 2), similar to the connectivity pat tern obtained for octahedral [(Mo 6 ) ] -clus ters in the structure of LiMo 6 Cl 13 [22]. The complete crystal structure of I contains an arrangement of cluster chains running along the y axis direction, forming layers in the x,y plane.…”

“…3 2012 EXPERIMENTAL Synthesis of WBr 6 [14]. Tungsten hexabromide was prepared by reacting W(CO) 6 with an excess of ele mental bromine. The W(CO) 6 (9.1 g, 0.0259 mol; Strem, 99%) was ground in an agate mortar under argon atmosphere (glovebox) and brought into a 250 mL Schlenk vessel.…”

“…The employment of bismuth as a reduction agent has brought up constitution isomers of BiW 6 Cl 15 ap pearing as (BiCl)[W 6 Cl 14 ] [3] and (BiCl 2 )[W 6 Cl 13 ] [4]. Corresponding reduction experiments were carried out with tungsten hexabromide to yield Bi 2 W 6 Br 18 [5].…”

“…When elemental red phosphorous was used as a reduc ing agent the interstitially stabilized phosphido cluster compound W 6 PCl 17 was obtained [6], which appears with an intermediate structure in between cluster ar chitectures of triprismo W 6 CCl 18 [7] and octahedro W 6 Cl 18 [8][9][10]. A chlorophosphinidene compound W 4 (PCl)Cl 10 [6] and a chlorocarbyne compound W 2 Cl 7 (CCl) [11] were also obtained via reduction with phosphorous and arsenic, the latter under solvother mal conditions.…”

Snap‐Shots of a Reduction Pathway: The Reaction of WCl6 with Copper Powder

“…Reactions of tungsten hexachloride with nonconventional reducing agents have revealed reductions at unexpectedly low temperatures, thereby producing new ternary compounds. Reactions of WCl 6 with elemental phosphorus or bismuth yielded phosphorus‐centered clusters W 6 PCl 17 and W 4 (PCl)Cl 10 or (BiCl)[W 6 Cl 14 ] and (BiCl) 2 [W 6 Cl 13 ], respectively , …”