Stoichiometric and Catalytic sp3 C-H/D2 Exchange Reactions of ortho-Substituted Benzenethiol and Phenols by a Ruthenium(II) Complex. Effect of a Chalcogen Anchor on

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• 作者：Masafumi Hirano ; Yuko Sakaguchi ; Toshiaki Yajima ; Naoki Kurata ; Nobuyuki Komine ; and Sanshiro Komiya
• 刊名：Organometallics
• 出版年：2005
• 出版时间：September 26, 2005
• 年：2005
• 卷：24
• 期：20
• 页码：4799 - 4809
• 全文大小：369K
• 年卷期：v.24,no.20(September 26, 2005)
• ISSN：1520-6041

文摘

A divalent thiaruthenacycle complex, cis-Ru[SC₆H₃(2-CH₂)(6-Me)-²S,C](PMe₃)₄ (3), isprepared by the treatment of Ru(⁴-1,5-COD)(⁶-1,3,5-COT) (1) with 2,6-dimethylbenzenethiolin the presence of PMe₃ via Ru(⁵-cyclooctadienyl)(SC₆H₃Me₂-2,6)(PMe₃)₂ (2). Exposure of 3in benzene to H₂ (0.1 MPa) leads to the quantitative formation of cis-RuH(SC₆H₃Me₂-2,6)(PMe₃)₄ (4), which readily turns to 3 at room temperature on evacuation, indicating thereversibility of the reaction. Both forward and backward reactions of this equilibrium areretarded by addition of PMe₃, suggesting prerequisite prior dissociation of PMe₃ for bothreactions. Complex 3 catalyzes selective and facile deuteration of the ortho-methyl and themercapto groups in 2,6-dimethylbenzenethiol under D₂.