New Method for the Synthesis of Octahedral Rhenium Chalcocyanide Cluster Complexes [{Re6(μ3-Q)8}(CN)6]4– (Q = S, Se, Te)

Abstract

A new method is proposed for the synthesis of the octahedral rhenium chalcocyanide cluster complexes [{Re₆(μ₃-Q)₈}(CN)₆]^4– (Q = S, Se, Te) using rhenium(IV) oxide as the starting compound. Among the synthesized compounds, the anhydrous cluster salt K₄[{Re₆Se₈}(CN)₆] is characterized by X-ray diffraction analysis for the first time. The crystals are orthorhombic, space group Pbcn; a = 13.1386(13), b = 11.4941(8), c = 17.2990(16) Å, Z = 4, V = 2612.4(4) ų (CIF file IСSD no. 434320). The crystal structure of K₄[{Re₆Se₈}(CN)₆] represents a framework type packing based on the K⁺ cations coordinated by the cyanide groups of the cluster anions [{Re₆Se₈}(CN)₆]^4–.