Ruthenium Complexes of Thiaporphyrin and Dithiaporphyrin

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• 作者：Chuan-Hung Chuang ; Chen-Kuo Ou ; Shan-Tung Liu ; Anil Kumar ; Wei-Min Ching ; Pei-Chun Chiang ; Mira Anne C. dela Rosa ; Chen-Hsiung Hung
• 刊名：Inorganic Chemistry
• 出版年：2011
• 出版时间：December 5, 2011
• 年：2011
• 卷：50
• 期：23
• 页码：11947-11957
• 全文大小：534K
• 年卷期：v.50,no.23(December 5, 2011)
• ISSN：1520-510X

文摘

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鈥搕hiaporphyrin through dechlorination and metathesis reactions. Accordingly, [Ru^II(STTP)(CO)X] (X = NO₃^鈥?/b> (2), NO₂^鈥?/b> (3), and N₃^鈥?/b> (4)) was synthesized and analyzed by single-crystal X-ray structural determination and NMR, UV鈥搗is, and FT-IR spectroscopic methods. An independent reaction of STPPH and [Ru(COD)Cl₂] led to [Ru^III(STTP)Cl₂] (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(S₂TTP)Cl₂] (S₂TTP = 5,10,15,20-tetratolyl-21,23-dithiaporphyrinato) with AgNO₃ and NaSePh, also via the metathesis strategy, resulted in novel dithiaporphyrin complexes [Ru^II(S₂TTP)(NO₃)₂] (6) and [Ru⁰(S₂TTP)(PhSeCH₂SePh)₂] (7), respectively. The structures of 6 and 7 were corroborated by X-ray crystallographic analyses. Complex 7 is an unprecedented ruthenium(0)鈥揹ithiaporphyrin with two bis(phenylseleno)methanes as axial ligands. A comparison of the analyses of the crude products from reactions of NaSePh and CH₂Cl₂ with or without [Ru(S₂TTP)Cl₂], further supported by UV鈥搗is spectral changes under stoichiometric reactions between [Ru(S₂TTP)Cl₂] and NaSePh, suggested a reaction sequence in the order of (1) formation of a putative [Ru^II(S₂TTP)(SePh)₂] intermediate, followed by (2) the concerted formation of PhSe鈥揅H₂Cl and simultaneously a reduction of Ru(II) to Ru(0) and finally (3) nucleophilic substitution of PhSeCH₂Cl by excess PhSe^{鈥?/sup>, resulting in PhSeCH₂SePh, which readily coordinated to the Ru(0) and completed the formation of bis(phenylseleno)methane complex 7.}