title: Ruthenium complexes of thiaporphyrin and dithiaporphyrin.
abstract: Successful synthesis and characterization of the six-coordinated complex [Ru(STTP)(CO)Cl] (1; STTP = 5,10,15,20-tetratolyl-21-thiaporphyrinato) allowed the development of the coordination chemistry of ruthenium-thiaporphyrin through dechlorination and metathesis reactions. Accordingly, [Ru(II)(STTP)(CO)X] (X = NO(3)(-) (2), NO(2)(-) (3), and N(3)(-) (4)) was synthesized and analyzed by single-crystal X-ray structural determination and NMR, UV-vis, and FT-IR spectroscopic methods. An independent reaction of STPPH and [Ru(COD)Cl(2)] led to [Ru(III)(STTP)Cl(2)] (5), which possessed a higher-valent Ru(III) center and exhibited good stability in the solution state. This stability allowed reversible redox processes in a cyclic voltammetric study. Reactions of [Ru(S(2)TTP)Cl(2)] (S(2)TTP = 5,10,15,20-tetratolyl-21,23-dithiaporphyrinato) with AgNO(3) and NaSePh, also via the metathesis strategy, resulted in novel dithiaporphyrin complexes [Ru(II)(S(2)TTP)(NO(3))(2)] (6) and [Ru(0)(S(2)TTP)(PhSeCH(2)SePh)(2)] (7), respectively. The structures of 6 and 7 were corroborated by X-ray crystallographic analyses. Complex 7 is an unprecedented ruthenium(0)-dithiaporphyrin with two bis(phenylseleno)methanes as axial ligands. A comparison of the analyses of the crude products from reactions of NaSePh and CH(2)Cl(2) with or without [Ru(S(2)TTP)Cl(2)], further supported by UV-vis spectral changes under stoichiometric reactions between [Ru(S(2)TTP)Cl(2)] and NaSePh, suggested a reaction sequence in the order of (1) formation of a putative [Ru(II)(S(2)TTP)(SePh)(2)] intermediate, followed by (2) the concerted formation of PhSe-CH(2)Cl and simultaneously a reduction of Ru(II) to Ru(0) and finally (3) nucleophilic substitution of PhSeCH(2)Cl by excess PhSe(-), resulting in PhSeCH(2)SePh, which readily coordinated to the Ru(0) and completed the formation of bis(phenylseleno)methane complex 7.
authors: Institute of Chemistry, Academia Sinica, Nankang, Taipei 115, Taiwan.
authors: Chuan-Hung
authors: CH
authors: Chuang
authors: Chen-Kuo
authors: CK
authors: Ou
authors: Shan-Tung
authors: ST
authors: Liu
authors: Anil
authors: A
authors: Kumar
authors: Wei-Min
authors: WM
authors: Ching
authors: Pei-Chun
authors: PC
authors: Chiang
authors: Mira Anne C
authors: MA
authors: dela Rosa
authors: Chen-Hsiung
authors: CH
authors: Hung
mesh_terms: D018360:Crystallography, X-Ray; D008024:Ligands; D008958:Models, Molecular; D008968:Molecular Conformation; D009566:Nitrates / Q000737:chemistry; D009570:Nitriles / Q000737:chemistry; D009573:Nitrites / Q000737:chemistry; D009942:Organometallic Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D011166:Porphyrins / Q000737:chemistry*; D012428:Ruthenium / Q000737:chemistry*; D013455:Sulfur / Q000737:chemistry*
chemical_list: D008024:Ligands; D009566:Nitrates; D009570:Nitriles; D009573:Nitrites; D009942:Organometallic Compounds; D011166:Porphyrins; D013455:Sulfur; D012428:Ruthenium