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      Platinum(II) phosphonate complexes derived from endo-8-camphanylphosphonic acid

      Leach, Meto T.; Henderson, William; Wilkins, Alistair L.; Lane, Joseph R.; Fortney-Zirker, Ryland G.; Turnbull, Mark M.; Nicholson, Brian K.
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      DOI
       10.1016/j.ica.2011.05.013
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       www.sciencedirect.com
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      Leach, M.T., Henderson, W., Wilkins, A.L., Lane, J.R., Fortney-Zirker, R.G., Turnbull, M.M. & Nicholson, B.K. (2011). Platinum(II) phosphonate complexes derived from endo-8-camphanylphosphonic acid. Inorganica Chimica Acta, available online 17 May 2011.
      Permanent Research Commons link: https://hdl.handle.net/10289/5437
      Abstract
      The reactions of cis-[PtCl₂L₂] [L = PPh₃, PMe₂Ph or L₂ = Ph₂P(CH₂)₂PPh₂ (dppe)] with endo-8-camphanylphosphonic acid (CamPO₃H₂) and Ag₂O in refluxing dichloromethane gave platinum(II) phosphonate complexes [Pt(O₃PCam)L₂]. The X-ray crystal structure of [Pt(O₃PCam)(PPh₃)₂]•₂CHCl₃ shows that the bulky camphanyl group, rather than being directed away from the platinum, is instead directed into a pocket formed by the Pt and the two PPh₃ ligands. This allows the O₃P–CH₂ group to have a preferred staggered conformation. The complexes were studied in detail by NMR spectroscopy, which demonstrates non-fluxional behaviour for the sterically bulky PPh₃ and dppe derivatives, which contain inequivalent phosphine ligands in their ³¹P NMR spectra. These findings are backed up by theoretical calculations on the PPh₃ and PPhMe₂ derivatives, which show, respectively, high and low energy barriers to rotation of the camphanyl group in the PPh₃ and PPhMe₂ complexes. The X-ray crystal structure of CamPO₃H₂ is also reported, and consists of hydrogen-bonded hexameric aggregates, which assemble to form a columnar structure containing hydrophilic phosphonic acid channels surrounded by a sheath of bulky, hydrophobic camphanyl groups.
      Date
      2011
      Type
      Journal Article
      Publisher
      Elsevier
      Collections
      • Science and Engineering Papers [3143]
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