Ruthenium(III) catalysed oxidation of l-leucine by a new oxidant, diperiodatoargentate(III) in aqueous alkaline medium

The kinetics of Ru(III) catalysed oxidation of l-leucine by diperiodatoargentate(III) (DPA) in alkaline medium at 298 K and a constant ionic strength of 0.60 mol dm−3 was studied spectrophotometrically. The oxidation products are pentanoic acid and Ag(I). The stoichiometry is [l-leucine]:[DPA] = 1:2. The reaction is of first order in Ru(III) and [DPA] and has less than unit order in both [l-leu] and [alkali]. The oxidation reaction in alkaline medium has been shown to proceed via a Ru(III)–l-leucine complex, which further reacts with one molecule of monoperiodatoargentate(III) (MPA) in a rate determining step followed by other fast steps to give the products. The main products were identified by spot test and spectral studies. The reaction constants involved in the different steps of the mechanism are calculated. The catalytic constant (Kc) was also calculated for the Ru(III) catalysed reaction at different temperatures. From the plots of log Kc versus 1/T, values of activation parameters with respect to the catalyst have been evaluated. The activation parameters with respect to the slow step of the mechanism are computed and discussed, and thermodynamic quantities are also determined. The active species of catalyst and oxidant have been identified.

The kinetics of oxidation of l-leucine by diperiodatoargentate(III) (DPA) in the presence of micro amounts of ruthenium(III) in alkaline medium has been studied. The active species of DPA is found to be [Ag(H2IO6)(H2O)2] and that of ruthenium(III) to be [Ru(H2O)5OH]2+ in alkaline medium.Figure optionsDownload as PowerPoint slide