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 [MoOS3]2- and [WS4]2- with Cudtp (dtp = diethyl
dithiophosphate) gave rise to the clusters [Bu4N]2[{MoOS3}4Cu12(dtp)6], 1, and [Et4N][{WS4Cu4}(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 [Mo2O2S6Cu6]2+ core and two incomplete cubane-like
[MoOS3Cu3]+ units. In cluster 2, the [WS4Cu4]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.