Synthesis of three-component high nuclearity cluster complexes with ruthenium carbido carbonyl clusters as a building block

Treatment of AgNO3 with the Rh–Ru and Cu–Ru hetero bimetallic clusters, [PPN][RhRu5C(CO)14(cod)] and [PPh4]2[CuRu6C(CO)16Cl], afforded novel three-component complexes having one silver-, and two silver-bridges between respective cluster units, [PPN]{Ag[RhRu5C(CO)14(cod)]2} and [PPh4]2{Ag2[CuRu6C(CO)16Cl]2}, respectively. Reaction of the ruthenium–copper cluster [PPh4]2{Cu4[Ru6C(CO)16]2Cl2} (6) with Pd2(dba)3 · CHCl3 gave another three-component cluster [PPh4]2{Cu4Pd2[Ru6C(CO)16]2Cl2} by incorporation of two palladium atoms. However, a similar reaction of 6 with Pt(dba)2 gave only a two-component cluster complex, [PPh4]2{Pt2[Ru6C(CO)15]2}, while the reaction of silver analog [PPN]2{Ag4[Ru6C(CO)16]2Cl2} with Pd2(dba)3 · CHCl3 resulted in the formation of known ruthenium–palladium cluster [PPN]2{Pd4[Ru6C(CO)16]2}. Treatment of 6 with [RhCl(CO)2]2 gave two two-component clusters, [PPh4][RhRu5C(CO)16] and [PPh4]2{Cu7[Ru6C(CO)15]2Cl3}. All the new mixed-metal high nuclearity clusters have been characterized by single crystal X-ray analyses.

Graphical abstractNew routes to high nuclearity cluster complexes that contain thee different metals have been explored. Cluster cores {Ag Rh Ru5} and {Ag Cu Ru6} were obtained by the reaction of Ag+ with [RhRu5C(CO)14(cod)]− and [CuRu6C(CO)16Cl]−, respectively. Eighteen nuclearity {Cu4 Pd2 Ru12} cluster was synthesized by the reaction of Pd2(dba)3 with {Cu4[Ru6C(CO)16]2Cl2}2−.Figure optionsDownload full-size imageDownload as PowerPoint slide