• D Bandyopadhyay

      Articles written in Journal of Chemical Sciences

    • Reactive intermediates in iron(III) porphyrin-catalyzed oxidation reactions

      P Wadhwani K Kamaraj D Bandyopadhyay

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      In iron(III) porphyrin-catalyzed oxidation of organic substrates by various monooxo transfer agents, oxoiron(IV) porphyrin cation radical(oxene) has been thought to be the most probable reactive intermediate. Our work, as reported here, indicates that oxo transfer to suitable substrates is possible by a distinctly different route. In case of MCPBA, the oxo transfer is very strongly solvent dependent. For example, in pure toluene solvent, intermediacy of oxene is not at all important, whereas in dichloromethane-methanol mixed solvent, the role of oxene is very significant. We also note that solvent molecules are susceptible to self oxidation by various oxidizing systems.

    • Iron(III) porphyrin-catalysed oxidation reactions by m-chloroperbenzoic acid: Nature of reactive intermediates

      A Agarwala V Bagchi D Bandyopadhyay

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      The reaction of m-chloroperbenzoic (m-CPBA) acid with meso-tetrakis (pentafluorophenyl) porphynatoiron(III) chloride (F20TPPFe(III)Cl ) has been studied in dichloromethane and acetonitrile medium at 25 ± 1°C. The reactive intermediates formed in this reaction have been quantitatively trapped by 2,4,6-tri t-butylphenol (TTBP) in both the solvents. It has been observed that the kinetic plots of the formation of TTBP radical in dichloromethane are all multiexponential, supporting the formation of more than one reactive intermediate in this solvent. In acetonitrile solvent the formation of TTBP radical was however observed to be distinctly single exponential. Different kinds of reactive intermediates are proposed in these two solvents.

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