The complexes with general formula mer-[RuCl3(dppb)(N)] [where dppb = 1,4-bis(diphenylphosphino)butane and N = pyridine (py), 4-methylpyridine (4-Mepy), 4-vinylpyridine (4-Vpy), 4-tert-butylpyridine (4-tBupy) and 4-phenylpyridine (4-Phpy)] were synthesized and characterized, and they were tested as catalytic precursor on the hydrogenation of cyclohexene. All five complexes are active in this kind of reaction, and they showed good conversion and acceptable TOF values. However, it was observed no dependence of N-donor groups coordinated to the metal center in the yields of the hydrogenated product, but the behavior of those complexes involves the activation of the precursor, owing to a reduction in situ of the complexes and the labilization of N-donor groups. The complex mer-[RuCl3(dppb)(4-Vpy)] was applied also in the aldehyde hydrogenation, showed good conversion and acceptable TOF values.