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Title: Homogeneous catalysis of aquachlororuthenium(III) complex and evaluation of individual kinetic and thermodynamic parameters of bromate-mandelic acid reaction
Authors: Reddy, Ch Sanjeeva
Kumar, T Vijaya
Issue Date: Jul-2006
Publisher: NISCAIR-CSIR, India
Abstract: Aquachlororuthenium(III) complex catalysed and uncatalysed acid bromate oxidation of mandelic acid (MA) is reported here. Uncatalyst oxidation exhibits first order each in [M A] and [bromate], and second order in [acid]. Primary kinetic isotope effect (kH/kD) = 1) has been found to be absent. However, an inverse solvent isotope effect is observed. The assumed mechanism includes slow formation of a mandelic ester of bromic acid due to the nucleophilic attack by the alcoholic/hydroxyl group at the bromine atom of HOBr+O(OH), which dissociates rapidly through C-C bond cleavage to form ben7.aldehyde and CO2. Aquachlororuthenium(III) complex catalysed MA-bromate reaction exhibits second order in [bromated], first order in [catalyst], fractional order in [MA] and a dualistic effect in [acid]. The envisaged mechanism involves complex formation between the substrate and the catalyst, which in turn forms a ternary complex with two moles of the oxidant. The slow decomposition of the ternary complex to form products constitutes the rate-determining step. The rate constants involved in each step of the reaction have been evaluated along with their thermodynamic parameters.
Page(s): 1611-1618
ISSN: 0975-0975(Online); 0376-4710(Print)
Appears in Collections: IJC-A Vol.45A(07) [July 2006]

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