Kinetics of Oxidation of Aniline and Xylidines by the Tetrahydroxoargentate(III) Ion

Article abstract of DOI:10.1246/bcsj.67.1207

The reactions of ^- with aniline and xylidines have been investigated.The stopped-flow experiments reveal kinetically distinguishable steps involving initial complexation of the substrate with the silver(III) species which is followed by its decomposition.The latter process obeys first-order kinetics and takes place with a rate constant of about 0.8 s^-1 through intramolecular electron transfer from substrate to the silver(III) center.Azobenzene and p-benzoquinone have been identified as the main products of the reaction of ^- and aniline.An increase in concentration of aniline enhances the yield of azobenzene which accounts for approximately 65percent of the consumed aniline.This effect has been interpreted by the increased effective complexation between aniline and ^- at higher concentrations.The stoichiometry of the reaction is found to vary with a change in the concentration of aniline.At higher concentrations it comes out to be 1:2 for ^-:aniline.A mechanism of this reaction is worked out.