The reaction of cis-[RuCl₂(dppb)(N–N)], dppb=1,4-bis(diphenylphosphino)butane, complexes with the ligand HSpymMe₂, 4,6-dimethyl-2-mercaptopyrimidine, yielded the cationic complexes [Ru(SpymMe₂)(dppb)(N–N)]PF₆, N–N=bipy (1) and Me-bipy (2), bipy=2,2′-bipyridine and Me-bipy=4,4′-dimethyl-2,2′-bipyridine, which were characterized by spectroscopic and electrochemical techniques and X-ray crystallography and elemental analysis. Additionally, preliminary in vitro tests for antimycobacterial activity against Mycobacterium tuberculosis H37Rv ATCC 27264 and antitumor activity against the MDA-MB-231 human breast tumor cell line were carried out on the new complexes and also on the precursors cis-[RuCl₂(dppb)(N–N)], N–N=bipy (3) and Me-bipy (4) and the free ligands dppb, bipy, Me-bipy and SpymMe₂. The minimal inhibitory concentration (MIC) of compounds needed to kill 90% of mycobacterial cells and the IC₅₀ values for the antitumor activity were determined. Compounds 1–4 exhibited good in vitro activity against M. tuberculosis, with MIC values ranging between 0.78 and 6.25μg/mL, compared to the free ligands (MIC of 25 to >50μg/mL) and the drugs used to treat tuberculosis. Complexes 1 and 2 also showed promising antitumor activity, with IC₅₀ values of 0.46±0.02 and 0.43±0.08μM, respectively, against MDA-MB-231 breast tumor cells.