Preparation and molecular structures of the decanuclear diynyl-ruthenium-silver and -copper complexes [M6{μ3-CCCC[Ru(dppe)Cp∗]}4(μ-dppm)2](BF4)2 (M = Ag, Cu)

Reactions between [M2(dppm)2(NCMe)2]X2 [M = Ag, X = ClO4; M = Cu, X = BF4] and Ru(CCCCM)(dppe)Cp∗ [M = Ag, Cu; generated in situ from Ru(CCCCH)(dppe)Cp∗ and AgNO3 or CuCl(PPh3), respectively] afford the cationic mixed-metal cluster diynyl complexes [M6{μ3-CCCC[Ru(dppe)Cp∗]}4(μ-dppm)2]X2, of which the structures were determined by single-crystal XRD studies. Electrochemical studies indicate that there is no interaction between the ruthenium centres. Reactions between [M2(μ-dppm)2(NCMe)2](BF4)2 and Ru(CCCCM′)(dppe)Cp∗ (M,M′ = Cu, Ag) afforded a mixture of Ag6−nCun clusters, as shown by ES-MS and crystallographic studies. Preliminary studies suggest that extensive disproportionation occurs in solution.

Graphical abstractReactions between [M2(dppm)2(NCMe)2]X2 [M = Ag, X = ClO4; M = Cu, X = BF4] and Ru(CCCCM′)(dppe)Cp∗ (M′ = Ag, Cu) afford the cationic mixed-metal cluster diynyl complexes [(MnM′6−n){μ3-CCCC[Ru(dppe)Cp∗]}4(μ-dppm)2]X2, as shown by ES–MS and crystallographic studies. Electrochemical studies indicate that there is no interaction between the ruthenium centres. Preliminary studies suggest that extensive disproportionation occurs in solution.Figure optionsDownload full-size imageDownload as PowerPoint slide