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.

Reactions 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 as PowerPoint slide