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Influence of copper(II) catalyst on the oxidation of L-histidine by platinum(IV) in alkaline medium: a kinetic and mechanistic study

Research Authors
Ahmed Fawzy
Research Abstract

The kinetics of oxidation of L-histidine (His) by platinum(IV) in the absence and presence of copper(II) catalyst was studied using spectrophotometry in alkaline medium at a constant ionic strength of 0.1 mol dm-3 and at 25 C. In both cases, the reactions exhibit a 1:1 stoichiometry ([His]:[PtIV]). The rate of the uncatalyzed reaction is dependent on the first power of each of the concentrations of oxidant, substrate and alkali. The catalyzed path shows a first-order dependence on both [PtIV] and [CuII], but the order with respect to both [His] and [OH-] is less than unity. The rate constants increase with increasing ionic strength and dielectric constant of the medium. The catalyzed reaction has been shown to proceed via formation of a copper(II)_ histidine intermediate complex, which reacts with the oxidant by an inner-sphere mechanism leading to decomposition of the complex in the rate-determining step. Platinum(IV) is reduced to platinum(II) by the substrate in a one-step two-electron transfer process. This is followed by other fast steps, giving rise to the oxidation products which were identified as 2-imidazole acetaldehyde, ammonia and carbon dioxide. A tentative reaction mechanism is suggested, and the associated rate laws are deduced. The activation parameters with respect to the slow step of the mechanism are reported and discussed.

Research Date
Research File
Research Journal
Transition Met Chem
Research Member
Research Publisher
Springer
Research Rank
2
Research Vol
39
Research Year
2014
Research Pages
567–576