Synthesis of Two New Rhenium Clusters [{Re8Se8(µ-O)3}(CN)18]8– and [{Re12S14}(CN)27]9–

The family of chalcogenide rhenium clusters is well represented in the literature by a series of compounds with different nuclearities, including heterometallic complexes. Here we report the synthesis and detailed characterization of new cyanide clusters [{Re₈Se₈(µ-O)₃}(CN)₁₈]^8– and [{Re₁₂S₁₄}(CN)₂₇]^9–. Both compounds were obtained by reactions of ReI₃, RuCl₃ and elemental selenium or sulfur with KCN at elevated temperatures, reflecting attempts to prepare heterometallic complexes with noble metals. The first cluster can be visualized as two fragments [{Re₄Se₄}(CN)₉]^– linked by three µ-O^2– bridging ligands. The second one can be represented as three tetrahedral [{Re₄S₄}(CN)₉]^– fragments linked by two µ₃-bridged sulfide ligands. Two of three {Re₄S₄} cores are additionally linked by direct Re–Re bond.