The New Binary Tungsten Iodide W₁₅I₄₇ 

Abstract

The new tungsten iodide W15I47 was synthesized by reacting tungsten hexacarbonyl with iodine under elevated pressure and temperature conditions. The structure of W15I47 was refined by single‐crystal X‐ray diffraction with the non‐centrosymmetric space group C2 [Z = 2, a = 4088.3(4) pm, b = 952.3(1) pm, c = 1198.5(2) pm, and β = 103.97(1)°]. The characteristic motif in the structure is the square pyramidal tungsten cluster that may be constructed from an octahedral [(W6I8i)I6a]2– cluster by removing one tungsten atom together with its outer iodide ligand to yield [(W5I8i)I5a]n–. The formula W15I47 represents three square pyramidal tungsten clusters with two of them being distinguishable in [(W5I8i)Ia(I3)2a(I3)2/2a–a][(W5I8i)I2a(I3)3/2a–a]2, by different numbers of iodide and tri‐iodide ligands at the cluster vertices.

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

“…1). A corresponding [(W 5 ) ] -frag ment is contained in the structure of W 15 I 47 [17] which contains outer mono iodide and tri iodide ligands, and in [(W 5 ) ] n-(n = 1, 2) [18]. Moreover, similar cluster compounds with a square pyramidal metal core were reported for molybdenum halides, such as for [Mo 5 Cl 13 ] n-(n = 1-3) [19][20][21].…”

Phosphorus‐Centered and Phosphinidene‐Capped Tungsten Chloride Clusters

“…[9] Recently, the reduction of WCl 6 with the metal bis- [11] At present, we are exploring the reduction of WCl 6 by using soft reducing agents and moderate heating temperatures (this temperature region is not often used) in order to explore the potentially largest field of missing compoundsthe thermally labile cluster compounds. [12] Over the course of systematic investigations with the employment of phosphorus as a reducing agent, we here present the novel cluster compounds W 6 PCl 17 and W 4 (PCl)Cl 10 , which represent the first examples of phosphorus-containing tungsten halide clusters. The WCl 6 reduction with elemental red phosphorus has been described before, but obviously under different conditions.…”

A Facile Method for the Synthesis of Binary Tungsten Iodides

“…[9] This most successful method was refreshed in ac omprehensive study for the preparation of tungsten iodides in 1995, [10] and also evaluated by us. [11] As part of these studies,r eactions were conducted in which W(CO) 6 was thermally decomposed with varying amounts of I 2 in ac losed glass vessel, or in af low of argon, at temperatures in excess of 140 8 8C. Despite the intrinsically low yields and the poor product homogeneities obtained from these reactions,several new tungsten iodide compounds could be characterized.…”