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Complexes of the general formulae [Ru(diamine)(PPh 3 )(η-C 5 H 5 )]ClO 4 and [Ru(diolefin)(PPh 3 )(η-C 5 H 5 )]ClO 4 (diamine = ethylenediamine (en), propylenediamine (pn), 2,2′-bipyridine (bipy), 1,10-phenanthroline (phen), biimidazole (H 2 bim), bibenzimidazole (H 2 bbzim) and 2-(2′-pyridylbenzimidazole) (Hpybzim); diolefin = 2,5-norbornadiene (nbd), tetrafluorobenzobarrelene (tfb)) have been made by reaction of the complex RuCl(PPh 3 ) 2 (η-C 5 H 5 ) with the diamine or diolefin in the presence of sodiuim perchlorate. A single-crystal X-ray diffraction study of [Ru(nbd)(PPh 3 )(η-C 5 H 5 )]ClO 4 has been carried out. Crystals of the complex are monoclinic, space group P 2 1 / n , with a 18.0576(5), b 14.5070(3), c 10.3186(3) A; β 103.20(6)°. The structure was solved by Patterson synthesis using 4209 observed reflections (2σ( I ) criterion) and refined to a R factor of 0.040. Reaction of RuCl(PPh 3 ) 2 (η-C 5 H 5 ) with oxygen in the presence of sodium perchlorate leads to oxidation of the coordinated triphenylphospine ligands giving the complex [Ru{(η 6 -C 6 H 5 )Ph 2 PO}η-C 5 H 5 )]ClO 4 . In order to establish the structural identity of this compound a single-crystal X-ray diffraction study has been made. Crystals of this complex are monoclinic, space group P 2 1 / c , with a 10.818(5), b 9.4480(3), c 21.0036(19) A; β 90.246(6)°. The structure was solved by Patterson synthesis using 3819 observed reflections (3σ( I ) criterion) and refined to a R factor of 0.036. The ruthenium atom is coordinated in a sandwich fashion by the cyclopentadienyl group and a phenyl ring of the triphenylphosphine oxide ligand. The synthesis of new heteronuclear ruthenium(II)-rhodium(I) complexes of formulae [(η-C 5 H 5 )(Ph 3 P)-Ru(μ-bim)RhY 2 ] x and (η-C 5 H 5 )(Ph 3 P)Ru(μ-bbzim)RhY 2 (Y = CO, Y 2 = diolefin) is also described.