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      Synthesis and characterisation of isomeric cycloaurated complexes derived from the iminophosphorane Ph₃P=NC(O)Ph

      Kilpin, Kelly Joan; Linklater, Rachael Annette; Henderson, William; Nicholson, Brian K.
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      Henderson 2010 isomeric.pdf
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      DOI
       10.1016/j.ica.2009.12.019
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      Kilpin, K.J., Linklater, R.A., Henderson, W. & Nicholson, B.K. (2010). Synthesis and characterisation of isomeric cycloaurated complexes derived from the iminophosphorane Ph₃P=NC(O)Ph. Inorganica Chimica Acta, 363(5), 1021-1030.
      Permanent Research Commons link: https://hdl.handle.net/10289/4364
      Abstract
      Using different organomercury substrates, two isomeric cycloaurated complexes derived from the stabilised iminophosphorane Ph₃P NC(O)Ph were prepared. Reaction of Ph₃P NC(O)Ph with PhCH₂Mn(CO)₅ gave the manganated precursor (CO)₄Mn(2-C₆H₄C(O)N PPh₃), metallated on the C(O)Ph substituent, which yielded the organomercury complex ClHg(2-C₆H₄C(O)N PPh₃) by reaction with HgCl₂ in methanol. Transmetallation of the mercurated derivative with Me₄N[AuCl₄] gave the cycloaurated iminophosphorane AuCl₂(2-C₆H₄C(O)N PPh₃) with an exo PPh₃ substituent. The endo isomer AuCl₂(2-C₆H₄Ph₂P NC(O)Ph) [aurated on a PPh₃ ring] was obtained by an independent reaction sequence, involving reaction of the diarylmercury precursor Hg(2-C₆H₄P( NC(O)Ph)Ph₂)₂ [prepared from the known compound Hg(2-C₆H₄PPh₂)₂ and PhC(O)N₃] with Me₄N[AuCl₄]. Both of the isomeric iminophosphorane derivatives were structurally characterised, together with the precursors (2-HgClC₆H₄)C(O)N PPh₃ and (CO)₄Mn(2-C₆H₄C(O)N PPh₃). The utility of ³¹P NMR spectroscopy in monitoring reaction chemistry in this system is described.
      Date
      2010
      Type
      Journal Article
      Publisher
      Elsevier
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      • Science and Engineering Papers [2925]
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