A monosubstituted decarbonylation reaction was performed on cis-,cis-[Ru{η 2 -N(O)C 1 0 H 6 O} 2 (CO) 2 ] (cis-NO, cis-O) (A), trans-,cis-[Ru{η 2 -N(O)C 1 0 H 6 O} 2 (CO) 2 ] (trans-NO, cis-O) (B), cis-,cis-[Ru{η 2 -OC 1 0 H 6 N(O)} 2 (CO) 2 ] (C), trans-,cis-[Ru{η 2 -OC 1 0 H 6 N(O)} 2 (CO) 2 ] (D) and cis-,trans-[Ru{η 2 -OC 1 0 H 6 N(O)} 2 (CO) 2 ] (cis-NO, trans-O) (E) with donor ligand (L) 4-phenylpyridine (ppy), 4-{2-(9-anthryl)vinyl}pyridine (avpy) or triphenylphosphine (PPh 3 ) to give substituted complex cis-,cis-[Ru{η 2 -N(O)C 1 0 H 6 O} 2 (CO)L] (1a, L=ppy; 2a, L=avpy; 3a, L=PPh 3 ), trans-,cis-[Ru{η 2 -N(O)C 1 0 H 6 O} 2 (CO)L] (1b, L=ppy), cis-,cis-[Ru{η 2 -OC 1 0 H 6 N(O)} 2 (CO)L] (1c, L=ppy; 2c, L=avpy), trans-,cis-[Ru{η 2 -OC 1 0 H 6 N(O)} 2 (CO)L] (1d, L=ppy; 2d L=avpy) or cis-,trans-[Ru{η 2 -OC 1 0 H 6 N(O)} 2 (CO)L] (1e, L=ppy). Progressive substitution of the carbonyl ligands of A by tributylphosphine (PBu 3 ) or functionalized pyridine 4-formylpyridine (fpy), 4-ethylpyridine (epy) or 4-dimethylaminopyridine (mapy) gave a centrosymmetric bisubstituted complex trans-,trans-[Ru{η 2 -N(O)C 1 0 H 6 O} 2 L 2 ] (8a, L=PBu 3 ; 9a, L=fpy; 10a, L=epy; 11a, L=mapy) together with the corresponding mono-CO-substituted complex cis-,cis-[Ru{η 2 -N(O)C 1 0 H 6 O} 2 (CO)L] (4a, L=PBu 3 ; 5a, L=fpy; 6a, L=epy; 7a, L=mapy). The electronic absorption spectra and metal-localized oxidation formal potentials changed significantly for the bisubstituted complexes compared with the monosubstituted ones.