The reaction of [RuCl3(AsPh3)(2)(MeOH)] with the dimeric complexes [(cod)RhCl](2), [(ppy)RhCl](2) (ppy = cyclometalated 2-phenylpyridine), [(cymene)RuCl2](2) and [CP*MCl2](2) (M = Rh, Ir) has been investigated. The structure of the resulting products was shown to depend on the reaction partner. Whereas for the rhodium complexes [(cod)RhCl](2) and [(ppy)RhCl](2), heterobimetallic compounds with two halogeno-bridges were found, the reactions with the halfsandwich complexes [(cymene)RuCl2](2) and [CP*MCl2](2) gave triply bridged products with concomitant formation of mononuclear [(pi-ligand)MCl2(AsPh3)] side products. The new complexes were all characterized by single crystal X-ray analysis. (C) 2004 Elsevier B.V. All rights reserved.