Ruthenium(III) Catalysis in Perborate Oxidation of 5-Oxoacids. (24th August 2014)

• Record Type: Journal Article
• Authors: Shree Devi, S.; Krishnamoorthy, P.; Muthukumaran, B.
• Other Names: An Taicheng Academic Editor.
• Is Part Of: Advances in physical chemistry. Volume 2014(2014)
• Publication Date: 2014-08-24
• Subjects: Chemistry, Physical and theoretical -- Periodicals; 541.05
• DOI: 10.1155/2014/879608
• Languages: English
• ISSNs: 1687-7985

Abstract

Abstract : Ruthenium(III) catalyzes perborate oxidation of substituted 5-oxoacids in acidic solution. The catalyzed oxidation is first order with respect to the oxidant and catalyst. The rate of ruthenium(III) catalyzed oxidation displays the Michaelis-Menten kinetics on the reductant and is independent of [H + ] of the medium. Hydrogen peroxide is the reactive species of perborate and the kinetic results reveal formation of ruthenium(III) peroxo species-5-oxoacid complex. Electron-releasing substituents accelerate the reaction rate and electron-withdrawing substituents retard it. The order of reactivity among the studied 5-oxoacids is p -methoxy≫ p -methyl > p -phenyl > −H > p -chloro > p -bromo > m -nitro. Activation parameters are evaluated using Arrhenius and Eyring's plots. A mechanism consistent with the observed kinetic data is proposed and discussed. A suitable rate law is derived based on the mechanism.