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

The preparation of thermally labile
compounds is a great temptation in chemistry which requires a careful
selection of reaction media and reaction conditions. With a new scanning
technique denoted here as Cluster Harvesting, a whole
series of metal halide compounds is detected by differential thermal
analysis (DTA) in fused silica tubes and structurally characterized
by X-ray powder diffraction. Experiments of the reduction of tungsten
hexahalides with elemental antimony and iron are presented. A cascade
of six compounds is identified during the reduction with antimony,
and five compounds or phases are monitored following the reduction
with iron. The crystal structure of Fe2W2Cl10 is reported, and two other phases in the Fe–W–Cl
system are discussed.