Improved synthetic routes to tungsten(IV) bromide complexes
Abstract Convenient synthetic routes to the compounds WBr4 (1), WBr4(MeCN)2 (2), WBr4(THF)2 (3), WBr4(PPh3)2 (4), WBr4(bpy) (6), and WBr4(dppe) (
Bhuiyan, Mohammad A. I.,Hargrove, Willie R.,Metz, Clyde R.,White, Peter S.,Sendlinger, Shawn C.
p. 613 - 621
(2015/08/06)
Cluster harvesting in the WBr6-P System
A combined thermal scanning-X-ray diffraction (XRD) approach was performed for the WBr6-P system to detect and analyze phases in this system, including metal-rich phases generated with increasing amounts of elemental (red) phosphorus under partial PBr3 release. Phases were characterized by powder XRD. A black crystalline powder of W4(PBr)Br10 was obtained after reduction of WBr6 with elemental phosphorus at 450 °C. The crystal structure of the new compound was found to be isotypic with the structure of W4(PCl)Cl10 on the basis of powder XRD data. The structure of W4(PBr)Br10 is represented by a cyclobutadiene-like tetranuclear tungsten cluster interconnected into a layered (W4(μ4-PBr)Br6i)Br8/2a-a arrangement via outer bromide ligands. The μ4-capping bromophosphinidene ligand was verified by solid-state magic-angle spinning 31P NMR spectroscopy.