The molybdenum and rhenium octahedral cluster chalcohalides in solid state chemistry: From condensed to discrete cluster units

The octahedral Mo-6 and Re-6 chalcohalides prepared by solid state routes at high temperature are reviewed from their origin to the recent period. Their crystal structures built from the face-capped M6L14 building blocks are presented according to the interunit connectivities, starting from the three-dimensional Chevrel phases and decreasing the dimensionality down to 2D, 1D and finally OD compounds in which the cluster units are discrete. In a second step, it is shown that the solid cluster compounds are relevant precursors for more recently expanded reactions in solution or by soft chemistry, giving access to a large variety of hybrid organic/inorganic cluster materials. (C) 2012 Academie des sciences. Published by Elsevier Masson SAS. All rights reserved.