Synthesis and characterisation of isomeric cycloaurated complexes derived from the iminophosphorane Ph3PNC(O)Ph |
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Authors: | Kelly J. Kilpin Brian K. Nicholson |
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Affiliation: | Department of Chemistry, University of Waikato, Private Bag 3105, Hamilton, New Zealand |
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Abstract: | Using different organomercury substrates, two isomeric cycloaurated complexes derived from the stabilised iminophosphorane Ph3PNC(O)Ph were prepared. Reaction of Ph3PNC(O)Ph with PhCH2Mn(CO)5 gave the manganated precursor (CO)4Mn(2-C6H4C(O)NPPh3), metallated on the C(O)Ph substituent, which yielded the organomercury complex ClHg(2-C6H4C(O)NPPh3) by reaction with HgCl2 in methanol. Transmetallation of the mercurated derivative with Me4N[AuCl4] gave the cycloaurated iminophosphorane AuCl2(2-C6H4C(O)NPPh3) with an exo PPh3 substituent. The endo isomer AuCl2(2-C6H4Ph2PNC(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)NPPh3 and (CO)4Mn(2-C6H4C(O)NPPh3). The utility of 31P NMR spectroscopy in monitoring reaction chemistry in this system is described. |
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Keywords: | Gold complexes Cyclometallated ligands Iminophosphoranes X-ray crystal structure Organomercury compounds |
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