Synthesis of Rhodium鈥揚rimary Thioamide Complexes and Their Desulfurization Leading to Rhodium Sulfido Cubane-Type Clusters and Nitriles

详细信息    查看全文

• 作者：Yuichiro Mutoh ; Masahiro Sakigawara ; Ippei Niiyama ; Shinichi Saito ; Youichi Ishii
• 刊名：Organometallics
• 出版年：2014
• 出版时间：October 13, 2014
• 年：2014
• 卷：33
• 期：19
• 页码：5414-5422
• 全文大小：577K
• ISSN：1520-6041

文摘

Although molecular thioamide complexes of late-transition metals have been prepared since 1979, the chemistry of primary thioamide complexes remains relatively unexplored. To shed light on this area, we have investigated synthesis, structures, and reactivities of simple rhodium organometallic complexes with a primary arenecarbothioamide ligand [Cp*RhCl₂{S鈺怌(Ar)NH₂-魏¹S}] (Cp* = 畏⁵-C₅Me₅). Intra- and intermolecular hydrogen bonding in the thioamide complexes is discussed on the basis of ¹H NMR spectroscopy and X-ray analysis. When these rhodium complexes were treated with a large excess amount of Et₃N, desulfurization of the thioamide ligand took place to give arenecarbonitriles (ArCN) in high GC yield and the cubane-type cluster [(Cp*Rh)₄(渭₃-S)₄] (3) in good yield as the organometallic product. Use of a smaller amount (2.4 equiv) of Et₃N followed by treatment with NaBAr^F₄ (Ar^F = 3,5-(CF₃)₂C₆H₃) led to the isolation of the cationic clusters [(Cp*Rh)₄(渭₃-S)₄](BAr^F₄) or [(Cp*Rh)₄(渭₃-S)₄](BAr^F₄)₂ in low yield. Reaction mechanisms of the desulfurization of the coordinated thioamides and the formation and one- or two-electron oxidation of 3 during the desulfurization are discussed.