The reaction of [RuCl3(AsPh3)(2)(MeOH)] with the dimeric complexes (cod)RhCl, (ppy)RhCl (ppy = cyclometalated 2-phenylpyridine), (cymene)RuCl2 and CP*MCl2 (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 and (ppy)RhCl, heterobimetallic compounds with two halogeno-bridges were found, the reactions with the halfsandwich complexes (cymene)RuCl2 and CP*MCl2 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.