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Free radical intervention, deamination and decarboxylation in the ruthenium(III)-catalysed oxidation of L-arginine by alkaline permanganate – a kinetic study

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Abstract

The kinetics of the RuIII catalysed oxidation of L-arginine by alkaline permanganate was studied spectrophotometrically using a rapid kinetic accessory. The reaction follows a two stage process. In both the stages the reaction is first order with respect to [oxidant] and [catalyst] with an apparent less than unit order in [substrate] and [alkali]. The data suggest that oxidation proceeds via formation of a complex between the active RuIII species and L-arginine, which then reacts with one mole of permanganate in a slow step to yield a L-arginine free radical, followed by a fast step to form the products. The reaction constants involved in the mechanism were evaluated. There is a good agreement between observed and calculated rate constants under different experimental conditions for both stages of reaction. The activation parameters for the slow step were calculated and are discussed.

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Halligudi, N.N., Desai, S.M. & Nandibewoor, S.T. Free radical intervention, deamination and decarboxylation in the ruthenium(III)-catalysed oxidation of L-arginine by alkaline permanganate – a kinetic study. Transition Metal Chemistry 26, 28–35 (2001). https://doi.org/10.1023/A:1007195304258

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