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2 Polish Journal of Chemical Technology

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Kinetics and mechanism of meso-tetraphenylporphyriniron(III) chloride (TPP) catalysed oxidation of indole by sodium perborate

Kungumathilagam D., Karunakaran K.

Polish Journal of Chemical Technology

2013

Vol. 15, nr 2

107–111

Developing catalyst is very significant for biologically important reactions which yield products, used as drugs. Mechanistic study on meso-tetraphenylporphyriniron(III) chloride (TPP) catalysed oxidation of indole by sodium perborate in aqueous acetic acid medium have been carried out. The reaction follows a fractional order with respect to substrate and catalyst. The order with respect to oxidant was found to be one. Increase in the percentage of acetic acid and increase in the concentration of [H+] decreased the rate. The reaction fails to initiate polymerization, and a radical mechanism is ruled out. Activation and thermodynamic parameters have been computed. A suitable kinetic scheme based on these observations has been proposed. Significant catalytic activity is observed for the reaction system in the presence of TPP.

Meso-tetraphenylporphyriniron(iii) chloride catalyzed oxidation of aniline and its substituents by magnesium monoperoxyphthalate in aqueous acetic acid medium

Raja M., Kulandaivelu K.

Polish Journal of Chemical Technology

2012

Vol. 14, nr 4

35-41

The catalytic properties of the fi rst generation catalyst meso-tetraphenylporphyriniron(III) chloride and magnesium monoperoxyphthalate (MMPP) as oxidant have been studied in the oxidation of aniline and its substituents in acetic acid medium. The thermodynamic parameters for the oxidation have been determined and discussed. It confi rms the Exner relationship (only at the low range of temperatures) and also some of the activation parameters to the isokinetic relationships. The magnesium monoperoxyphthalate oxidation with 18 ortho- meta- and para-substituted anilines fulfi lls with isokinetic relationship but not to any of the linear free energy relationships. The reaction mechanism and the rate law were proposed.