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      Monocations of bismuth and indium in arene media: A spectroscopic and EXAFS investigation

      Kuznetsov, Alexei N.; Popovkin, Boris A.; Henderson, William; Taylor, Michael J.; Bengtsson-Kloo, Lars
      DOI
       10.1039/b001130o
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      Kuznetsov, A. N., Popovkin, B. A., Henderson, W., Taylor, M. J., & Bengtsson-Kloo, L. (2000). Monocations of bismuth and indium in arene media: A spectroscopic and EXAFS investigation. Journal of Chemical Society Dalton Transactions, 1777-1781.
      Permanent Research Commons link: https://hdl.handle.net/10289/3419
      Abstract
      The composition of In–GaCl₃–benzene and In–BiCl₃–GaCl₃–benzene solutions was investigated by Raman, UV/Vis, 71Ga and 115In NMR spectroscopy as well as by X-ray absorption fine structure spectroscopy (EXAFS). Indium metal was found to be soluble in GaCl₃–benzene solution at room temperature through the reduction of GaIII, producing Ga⁺ and In⁺ species. The subvalent cations are likely to be stabilized by the interaction with benzene. The use of these solutions as reducing media for BiCl₃ leads to the formation of Bi₅3⁺ polycations, with Bi⁺ as an intermediate product. No other subvalent bismuth species were detected. Multinuclear NMR experiments show that the reducing agent is Ga⁺ rather than In⁺. Indium K-edge EXAFS data recorded from solutions without and with subvalent bismuth species present show that In⁺ is co-ordinated by benzene (at about 2.9 Å) and chlorine atoms from chlorometalate anions (at about 3.3 Å) in a formal ratio of 1 2. Electrospray mass spectroscopic data show that In+ is most likely co-ordinated by one arene molecule.
      Date
      2000
      Type
      Journal Article
      Publisher
      ROYAL SOC CHEMISTRY
      Collections
      • Science and Engineering Papers [3143]
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