Monometallic nitrosyl thiolate-thiol complexes of the form (por)Ru(NO)(S(CH2)(n)SH) (por = TPP, n = 2; TTP, n = 2-4) have been prepared in 49-61% isolated yields from the reaction of the (por)Ru(NO)(O-i-C5H11) alkoxide precursors with HS(CH2)(n)SH. The (OEP)Ru(NO)(SCH2CH2SH) complex was prepared in 71% isolated yield via addition of HSCH2CH2SNO to (OEP)Ru(CO). These (por)Ru(NO)(S(CH2)(n)SH) complexes have been fully characterized by elemental analyses, infrared and H-1 NMR spectroscopy, and by mass spectrometry. The molecular structure of (OEP)Ru(NO)(SCH2CH2SH) has been determined by single-crystal X-ray crystallography. The Ru-N-O moiety is linear with a bond angle of 170.9(9)degrees. The symmetrical bimetallic [(por)Ru(NO)](2)(mu-S(CH2)(n)S-S,S') complexes (por(1) = port; i.e., TPP/TPP, TTP/TTP, OEP/OEP) have also been prepared by variations of the procedures used in the preparation of their monometallic derivatives, and they have been fully characterized by elemental analyses, infrared and H-1 NMR spectroscopy, and by mass spectrometry. The novel unsymmetric [(TPP)-Ru(NO)](mu-SCH2CH2S-S,S')[Ru(NO)(OEP)] complex has also been obtained, and the experimental and simulated 1H NMR spectrum of the protons of the mu-dithiolate bridge indicate that all four protons are inequivalent.