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      https://www.ias.ac.in/article/fulltext/jcsc/111/03/0443-0452

    • Keywords

       

      Kinetics; manganese; oxidation; thiosulphate; nitrite; hydrogen peroxide; hydrazine

    • Abstract

       

      The dioxo-bridged MnIIIMnIV complexes [MnIIIMnIV(μ-O)2L4]3+(13+, L=bipy=2,2′-bipyridine; 23+, L=phen=1,10-phenanthroline) can be stabilized in aqueous solutions containing excess L in the rangepH 4–6. Thus stabilized in solution, the parent complex coexists only with its aqua derivative [MnIIIMnIV(μ-O)2L3(H2O)2]3+ (1a3+ for L=bipy;2a3+ for L=phen) in rapid equilibrium. The solutions are novel oxidants and quantitatively oxidize NO2 to NO3, S2O32− to S4O62−, H2O2 to O2 and N2H5+ to N2. Simple first-order kinetics is observed except in reactions of the bipy complex with NO2, H2O2 and in the reaction of the phen complex with N2H5+. Reaction of the bipy complex with NO2 produces the one-electron reduced intermediate1a2+, while H2O2 gives the two-electron reduced intermediate [MnIII(bipy)2(OH)(H2O)]2+. It is concluded that (a) the aqua complexes are kinetically more active than their parents, (b) the phen complexes react slower than the bipy-complexes, (c) Mn2+ has no catalytic role, but intermediate manganese complexes and radical species may act as autocatalysts, (d) outer-sphere one-electron transfer occurs generally, but H2O2 prefers a two-electron pathway in its reactions with the dimers, (e) nuclearity is retained until one of the manganese in the dimers is reduced to the +2 state.

    • Author Affiliations

       

      Rupendranath Banerjee1 Utpal Roy Choudhury1 Soumen Banerjee1

      1. Department of Chemistry, Jadavpur University, Calcutta - 700 032, India
    • Dates

       
  • Journal of Chemical Sciences | News

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