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  • Chem Sci Trans., 2015, 4(2),  pp 337-346  

    DOI:10.7598/cst2015.998

    Research Article

    Oxidorhenium(V) and Imidorhenium(V) Complexes of Pyridylpyridazine:Oxygen Atom Transfer, Oxidation and Substitution Involving Oxido, Phosphine Oxide and Phosphine Coordination

  • BIKASH KUMAR PANDA1, UMASANKAR SENAPATI2, BISWARUP MONDAL3 and SUMAN SENGUPTA4*
  • 1Department of Chemistry, Jangipur College, Jangipur, Murshidabad-742213, W.B., India
    2Department of Chemistry, Santipur College, Santipur, Nadia-741404, W.B., India
    3Department of Chemistry, Sitananda College, Nandigram, Purba Medinipur-721631, India
    4Department of Chemistry, Ananda Chandra College, Jalpaiguri-735101, W.B., India
  • Abstract

    Oxido and imido complexes of type ReVOCl3(dppz) and ReV(NPh)Cl3(dppz) having meridional geometry (where dppz is 3,6-di(2-pyridyl)pyridazine) have been isolated and characterized. The oxygen atom transfer from ReVOCl3(dppz) to PPh3 has afforded ReIII(OPPh3)Cl3(dppz) which on chemical oxidation by HNO3 yielded [ReIV(OPPh3)Cl3(dppz)]ReO4. Treatment of ReIII(OPPh3)Cl3(dppz) with PPh3 has furnished facial ReIII(PPh3)Cl3(dppz). The second-order rate law and large negative entropy of activation (-15.8 eu) of the oxygen atom transfer reaction of ReVOcl3(dppz) with PPh3 is consistent with an associative pathway initiating through nucleophilic phosphine attack to Re≡O π * orbitals.

    Keywords

    Oxidorhenium(V), Imidorhenium(V), Pyridylpyridazine, Oxygen atom transfer

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