Cluster harvesting in the WBr6-P system.
A combined thermal scanning-X-ray diffraction (XRD) approach was performed for the WBr(6)-P system to detect and analyze phases in this system, including metal-rich phases generated with increasing amounts of elemental (red) phosphorus under partial PBr(3) release. Phases were characterized by powder XRD. A black crystalline powder of W(4)(PBr)Br(10) was obtained after reduction of WBr(6) with elemental phosphorus at 450 °C. The crystal structure of the new compound was found to be isotypic with the structure of W(4)(PCl)Cl(10) on the basis of powder XRD data. The structure of W(4)(PBr)Br(10) is represented by a cyclobutadiene-like tetranuclear tungsten cluster interconnected into a layered (W(4)(μ(4)-PBr)Br(6)(i))Br(8)/(2)(a-a) arrangement via outer bromide ligands. The μ(4)-capping bromophosphinidene ligand was verified by solid-state magic-angle spinning (31)P NMR spectroscopy.
Section of Solid State and Theoretical Inorganic Chemistry, Institute of Inorganic Chemistry, Eberhard Karls University Tübingen , Auf der Morgenstelle 18, D-72076 Tübingen, Germany.
Markus
M
Ströbele
Klaus
K
Eichele
Hans-Jürgen
HJ
Meyer