title: Synthesis and Characterization of Thiolate-Thiol Complexes of Ruthenium Nitrosyl Porphyrins and Their Symmetrical and Unsymmetrical Dithiolate-Bridged Bimetallic Derivatives.
abstract: Monometallic nitrosyl thiolate-thiol complexes of the form (por)Ru(NO)(S(CH(2))(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-C(5)H(11)) alkoxide precursors with HS(CH(2))(n)()SH. The (OEP)Ru(NO)(SCH(2)CH(2)SH) complex was prepared in 71% isolated yield via addition of HSCH(2)CH(2)SNO to (OEP)Ru(CO). These (por)Ru(NO)(S(CH(2))(n)()SH) complexes have been fully characterized by elemental analyses, infrared and (1)H NMR spectroscopy, and by mass spectrometry. The molecular structure of (OEP)Ru(NO)(SCH(2)CH(2)SH) 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)(&mgr;-S(CH(2))(n)()S-S,S') complexes (por(1) = por(2); 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 (1)H NMR spectroscopy, and by mass spectrometry. The novel unsymmetric [(TPP)Ru(NO)](&mgr;-SCH(2)CH(2)S-S,S')[Ru(NO)(OEP)] complex has also been obtained, and the experimental and simulated (1)H NMR spectrum of the protons of the &mgr;-dithiolate bridge indicate that all four protons are inequivalent.
authors.affiliation: Department of Chemistry and Biochemistry, University of Oklahoma, 620 Parrington Oval, Norman, Oklahoma 73019.
authors.forename: Jonghyuk
authors.initials: J
authors.lastname: Lee
authors.forename: Geun-Bae
authors.initials: GB
authors.lastname: Yi
authors.forename: Masood A.
authors.initials: MA
authors.lastname: Khan
authors.forename: George B.
authors.initials: GB
authors.lastname: Richter-Addo