Preparation of Rhodium Pentasulfido(2−) Complexes with Hydrotris(3,5-dimethylpyrazol-1-yl)borato Coligand

Abstract

Treatment of [Tp*Rh(coe)(MeCN)] (Tp* = hydrotris(3,5-dimethylpyrazol-1-yl)borate; coe = cyclooctene) with S8 in MeCN afforded a complex with a chelating pentasulfido(2−) ligand [Tp*Rh(S5)(MeCN)], which was converted further to [Tp*Rh(S5)(CNXy)] (3; Xy = 2,6-Me2C6H3) by the reaction with XyNC. An X-ray analysis was carried out for 3, which disclosed a chair conformation for the RhS5 ring.

Addition of benzenethiol to terminal alkynes catalyzed by hydrotris(3,5-dimethylpyrazolyl)borate–Rh(III) bis(thiolate) complex: Mechanistic studies with characterization of the key intermediate

“…The Rh-N bond at the trans position of XyNC in 3 at 2.132(2) Å is much longer than that trans to MeCN at 2.056(3) Å in 2 0 , while the other corresponding Rh-S and Rh-N distances are not significantly different between 3 and 2 0 . Linear structure of the Rh-C-N-Xy linkage and the C"N stretching frequency are in good agreement with those of [Tp * Rh(g 2 -S 5 )(XyNC)] (m N"C at 2187 cm À1 ) [23].…”