868258-00-8Relevant academic research and scientific papers
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 the bond cleavage reaction
Hirano, Masafumi,Sakaguchi, Yuko,Yajima, Toshiaki,Kurata, Naoki,Komine, Nobuyuki,Komiya, Sanshiro
, p. 4799 - 4809 (2005)
A divalent thiaruthenacycle complex, ds-Ru[SC6H 3(2-CH2)(6-Me)-κ2S,C](PMe 3)4 (3), is prepared by the treatment of Ru(η4-1,5-COD)(η6-1,3,5-COT) (1) with 2,6-dimethylbenzenethiol in the presence of PMe3 via Ru(η5-cyclooctadienyl)(SC6H3Me 2-2,6)(PMe3)2 (2). Exposure of 3 in benzene to H2 (0.1 MPa) leads to the quantitative formation of cis-RuH(SC 6H3Me2-2,6)-(PMe3)4 (4), which readily turns to 3 at room temperature on evacuation, indicating the reversibility of the reaction. Both forward and backward reactions of this equilibrium are retarded by addition of PMe3, suggesting prerequisite prior dissociation of PMes for both reactions. Complex 3 catalyzes selective and facile deuteration of the ortho-methyl and the mercapto groups in 2,6-dimethylbenzenethiol under D2.
