Heterometallic Re/Mo and Re/W cubane-type cluster complexes

A series of heterometallic tetrahedral cluster complexes with the general formula [{MxRe4-xSe4}(CN)12]n– (M = Mo, W; x = 2, 3) was obtained using the reactions ReI3, MO3 with selenium and KCN at elevated temperatures. Compounds [ReW3Se4(CN)12]6– and [Re2W2Se4(CN)12]6– are the first rhenium-tungsten heterometallic clusters. Crystal structures, electrochemical properties in aqueous solutions and magnetic properties of crystalline samples have been studied in detail. It has been shown that new cluster anions demonstrate a regular change in geometric characteristics and redox potentials depending on the composition of the cluster core.