Construction of a novel Mo/Cu/S cluster with a closed double-cubane-like polyhedron and a chain polymer of W/Cu/S clusters

Reaction of MoOS(3)](2)(-) and WS(4)](2)(-) with Cudtp (dtp = diethyl dithiophosphate) gave rise to the clusters Bu(4)N](2)(MoOS(3))(4)Cu(12)(dtp)(6)], 1, and Et(4)N](WS(4)Cu(4))(dtp)(3)], 2, respectively. In cluster 1, the dtp- ligands act as both monodentate and bidentate ligands that bridge between Cu atoms and link together a closed double-cubane-like Mo(2)O(2)S(6)Cu(6)](2+) core and two incomplete cubane-like MoOS(3)Cu(3)]+ units. In cluster 2, the WS(4)Cu(4)](2+) fragments were connected via bidentate and doubly bridging dtp- bridges to give a chain polymeric anion. Cluster 1 is the first example of a Mo/Cu/S cluster that contains a closed double-cubane-like structure. Compound 2 is also rare and the first W/Cu/S polymer with dtp- linkages.