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      Permanent link:
      https://www.ias.ac.in/article/fulltext/jcsc/104/05/0603-0610

    • Keywords

       

      Phosphorous oxyacids; pyridinium hydrobromide perbromide; oxidation mechanism; kinetic isotope effect

    • Abstract

       

      Oxidation of three lower oxyacids of phosphorus, viz. phosphinic, phenylphosphinic and phosphorous acids by pyridinium hydrobromide perbromide (PHPB), is first-order with respect to both oxyacid and PHPB. There is no effect on addition of acylonitrile and pyridinium bromide. On oxidation, deuterated phosphinic and phosphorous acids exhibit substantial kinetic isotope effects. The effect of solvent composition on reaction rate indicates that the transition state is more polar than the reactants. Reaction rates were determined at different temperatures and the activation parameters calculated. Alternative mechanisms, involving the two tautomeric forms of the oxyacid, have been formulated and it has been concluded that the reaction proceeds through the pentacoordinated tautomer. Transfer of a hydride ion from the oxyacid to PHPB, in the rate-determining step, has been proposed.

    • Author Affiliations

       

      Seema Varshney1 Pradeep K Sharma1 Kalyan K Banerji1

      1. Department of Chemistry, JNV University, Jodhpur - 342005, India
    • Dates

       
  • Journal of Chemical Sciences | News

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