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

DOI Web Site Research Data 2 Citations 111 References
  • Yuichiro Mutoh
    Department of Applied Chemistry, Faculty of Science and Engineering, Chuo University, 1-3-27 Kasuga, Bunkyo-ku, Tokyo 112-8551, Japan
  • Masahiro Sakigawara
    Department of Applied Chemistry, Faculty of Science and Engineering, Chuo University, 1-3-27 Kasuga, Bunkyo-ku, Tokyo 112-8551, Japan
  • Ippei Niiyama
    Department of Applied Chemistry, Faculty of Science and Engineering, Chuo University, 1-3-27 Kasuga, Bunkyo-ku, Tokyo 112-8551, Japan
  • Shinichi Saito
    Department of Chemistry, Faculty of Science, Tokyo University of Science, 1-3 Kagurazaka, Shinjuku-ku, Tokyo 162-8601, Japan
  • Youichi Ishii
    Department of Applied Chemistry, Faculty of Science and Engineering, Chuo University, 1-3-27 Kasuga, Bunkyo-ku, Tokyo 112-8551, Japan

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Description

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═C(Ar)NH2-κ1S}] (Cp* = η5-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(μ3-S)4] (3) in good yield as the organometallic product. Use of a smaller amount (2.4 equiv) of Et3N followed by treatment with NaBArF4 (ArF = 3,5-(CF3)2C6H3) led to the isolation of the cationic clusters [(Cp*Rh)4(μ3-S)4](BArF4) or [(Cp*Rh)4(μ3-S)4](BArF4)2 in low yield....

Journal

  • Organometallics

    Organometallics 33 (19), 5414-5422, 2014-09-23

    American Chemical Society (ACS)

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