Kinetics and mechanism of the Ir(III)-catalyzed oxidation of xylose and maltose by potassium iodate in aqueous alkaline medium

For the first time, the Ir(III) catalysis of the iodate oxidation of xylose and maltose in aqueous alkaline medium has been investigated. The reactions exhibit first-order kinetics with respect to lower [IO3-] and [OH−] and show zero-order kinetics at their higher concentrations. Unity order at low concentrations of maltose becomes zero order at its higher concentrations, whereas zero-order kinetics with respect to [xylose] was observed throughout its variation. The reaction rate is found to be directly proportional to [Ir(III)] in the oxidation of both reducing sugars. Negligible effect of [Cl−] and nil effect of ionic strength (μ) on the rate of oxidation have also been noted. The species, [IrCl3(H2O)2OH]− was ascertained as the reactive species of Ir(III) chloride for both the redox systems. Various activation parameters have been calculated. Formic acid and arabinonic acid for maltose and formic acid and threonic acid for xylose were identified as the main oxidation products of the reactions. Mechanisms consistent with the observed kinetic data and spectral evidence have been proposed for the oxidation of xylose and maltose.

Graphical abstractIt is proposed that the Ir(III)-catalyzed oxidation of xylose and maltose takes place through the formation of a most unstable activated complex, , and the activated complex, , respectively.Figure optionsDownload full-size imageDownload as PowerPoint slideFigure optionsDownload full-size imageDownload as PowerPoint slide