W₄Br₁₀ Cluster Intermediates in the Solid State Nucleation of W₆Br₁₂

Abstract

The new adduct W 4 Br 10 ·2SbBr 3 and the new binary compound W 4 Br 10 were obtained as products in a reaction cascade in which WBr 6 was reacted with elemental antimony at successively increased temperatures. The crystal structures of both compounds were refined from X-ray powder diffraction data and their electronic struc-

Cluster Harvesting by Successive Reduction of a Metal Halide with a Nonconventional Reduction Agent: A Benefit for the Exploration of Metal-Rich Halide Systems

“…During the reaction progress, large crystals of SbBr 3 were growing in the silica container. This study represents an example for the investigation of the binary tungsten bromide system including some SbBr 3 adducts with tetrahedral, 15 square pyramidal, 16 and octahedral 17 metal atom cores. It can be seen that smaller clusters behave thermally labile, showing increasing cluster nuclearities and the conversion into an octahedral cluster with increasing temperature.…”

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

“…whereby tungsten is gradually reduced from the oxidation state +6 to +2. [4] More recently, the reduction of WCl 6 was explored with transition-metal powders such as Mn, Fe and Co. [5][6][7] Crystal structures of compounds appearing in these systems were refined by means of single-crystal and powder X-ray diffraction. More extensive studies were performed for compounds appearing in the Fe/W/Cl system, including electronic structure calculations, magnetic measurements, energy-dispersive X-ray spectroscopy (EDX) and Mössbauer spectroscopy.…”

“…Tungsten hexahalides turned out as promising starting materials, because tungsten ions may be reduced by various elements. The reduction of WBr 6 with antimony powder results in a cascade of intermediate products until W 6 Br 12 is formed, whereby tungsten is gradually reduced from the oxidation state +6 to +2 . More recently, the reduction of WCl 6 was explored with transition‐metal powders such as Mn, Fe and Co .…”

Cluster Harvesting in the WBr6–P System

“…This thermal scanning approach has been successfully employed to detect numerous compounds in the M–W–Cl system with M = Fe, Co, and Mn, and phases in the Sb–W–Br system. , …”

“…This thermal scanning approach has been successfully employed to detect numerous compounds in the M−W−Cl system with M = Fe, 1 Co, 2 and Mn, 3 and phases in the Sb−W− Br system. 1,4 Recently, the reduction of WCl 6 with phosphorus in a fusedsilica tube yielded the new compounds W 6 PCl 17 and W 4 (PCl)-Cl 10 , 5 of which the first compound represents a new type of hexanuclear phosphorus-centered W 6 cluster, which can be considered as a structural intermediate between the (empty) W 6 Cl 18 , 6 and the carbon-centered W 6 CCl 18 -type cluster. 7 The discovery of W 6 PCl 17 was indeed guided by serendipity (and persistence) because its thermal stability range (under the reaction conditions used) is approximately between 410 °C (formation) and 440 °C (decomposition).…”