Preparation and molecular structures of the decanuclear diynyl-ruthenium-silver and -copper complexes [M6{l3-C„CC„C[Ru(dppe)Cp*]}4(l-dppm)2](BF4)2(M = Ag, Cu)

Abstract

Reactions between [M2(dppm)2(NCMe)2]X2 [M = Ag, X = ClO4; M = Cu, X = BF4] and Ru(C{triple bond, long}CC{triple bond, long}CM)(dppe)Cp* [M = Ag, Cu; generated in situ from Ru(C{triple bond, long}CC{triple bond, long}CH)(dppe)Cp* and AgNO3 or CuCl(PPh3), respectively] afford the cationic mixed-metal cluster diynyl complexes [M6{μ3-C{triple bond, long}CC{triple bond, long}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{triple bond, long}CC{triple bond, long}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. © 2010 Elsevier B.V. All rights reserved.