Osmium(VIII) catalyzed oxidation of a sulfur containing amino acid—a kinetics and mechanistic approach

Abstract

The kinetics of osmium (VIII) catalyzed oxidation of DL-methionine by hexacyanoferrate(III) (HCF) in aqueous alkaline medium at a constant ionic strength of 0.50 mol dm⁻³ was studied spectrophoto-metrically. The reaction between hexacyanoferrate(III) and DL-methionine in alkaline medium exhibits 2:1 stoichiometry (2HCF:DL-methionine). The reaction is of first order each in [HCF] and [Os(VIII)], less than unit order in [alkali] and zero order for [DL-methionine]. The decrease in dielectric constant of the medium increases the rate of the reaction. The added products have no effect on the rate of reaction. The main products were identified by spot test. A free radical mechanism has been proposed. In a prior equilibrium step Os(VIII) binds to OH⁻ species to form a hydroxide species and reacts with [Fe(CN)₆]³⁻ in slow step to form an intermediate species(C₁). This reacts with a molecule of DL-methionine in a fast step to give the sulfur radical cation of methionine and yields the sulfoxide product by reacting with another molecule of [Fe(CN)₆]³⁻. The rate constant of the slow step of the mechanism is calculated. The activation parameters with respect to slow step of the mechanism are evaluated and discussed.

Keywords:

• Hexacyanoferrate(III)
• DL-methionine
• Kinetics and mechanism
• Kinetics
• Oxidation

Acknowledgements

One of the authors, S. M. Tuwar, thanks the UGC, Regional Office Bangalore, for providing financial assistance.