The cyclometalated complexes [Pt(ppy)R(SMe(2))] or [Pt(bhq)R(SMe(2))], where ppyH = 2-phenylpyridine, bhqH = benzo[h]quinoline and R = methyl or p-tolyl, react with bis(diphenylphosphino)ethane, dppe, in a 1:1 ratio to give the corresponding complexes [Pt(κ(1)-C-ppy)R(dppe)] or [Pt(κ(1)-C-bhq)R(dppe)], in which the ppy or bhq ligands are monodentate and dppe is chelating. The similar reaction in a 2:1 ratio gives the binuclear complexes [{Pt(ppy)R}(2)(μ-dppe)] or [{Pt(bhq)R}(2)(μ-dppe)], in which the dppe ligands are in the unusual bridging bidentate bonding mode.