• Kinetics and mechanism of the oxidation of phosphinic, phenylphosphinic and phosphorous acids by benzyltrimethylammonium dichloroiodate

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      https://www.ias.ac.in/article/fulltext/jcsc/109/02/0147-0154

    • Keywords

       

      Phosphorus oxyacids; kinetic isotope effect; benzyltrimethylammonium dichloroiodate

    • Abstract

       

      Oxidation of lower phosphorus oxyacids by benzyltrimethylammonium dichloroiodate (BTACI), in the presence of zinc chloride, resulted in the formation of the corresponding oxyacids with phosphorus in a higher oxidation state. The reaction is first order with respect to the concentration of BTACI, oxyacid and zinc chloride. The reaction exhibited the presence of a substantial kinetic isotope effect. Addition of benzyltrimethylammonium chloride enhances the reaction rate. It is proposed that the reactive oxidizing species is [PhCH2Me3N]+ [Zn2Cl6]−2I+. It has been shown that the pentacoordinated tautomer of the phosphorus oxyacid is the reactive reductant. A mechanism involving a hydride-ion transfer from the P-H bond to the oxidant in the rate-determining step has been postulated.

    • Author Affiliations

       

      Deepa Suri1 Seema Kothari1 Kalyan K Banerji1

      1. Department of Chemistry, J N V University, Jodhpur - 342 005, India
    • Dates

       
  • Journal of Chemical Sciences | News

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