Reactions between [M2(dppm)2(NCMe)2]X2 [M = Ag, X = ClO₄; M = Cu, X = BF₄] and Ru(C CC CM)(dppe)Cp* [M = Ag, Cu; generated in situ from Ru(C CC CH)(dppe)Cp* and AgNO₃ or CuCl(PPh₃), respectively] afford the cationic mixed-metal cluster diynyl complexes [M₆{μ₃-C CC C[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(C CC CM′)(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.