Kinetics of hexachloroplatinate(IV) (HCP) oxidation of L-histidine (His) in H2SO4 medium has been investigated in the absence and presence of silver(I) catalyst at constant ionic strength 2.0 mol dm-3 and temperature 25 C. The progress of both uncatalyzed and silver(I)-catalyzed oxidation reactions has been monitored spectrophotometrically. Both uncatalyzed and catalyzed paths show first-order dependence on [HCP] and fractionalfirst-order dependence each on [His] and [acid]. The catalyzed path is first order in [AgI ]. Increasing ionic strength and dielectric constant decreases the oxidation rates. The catalyzed reaction has been shown to proceed via formation of a silver(I)-histidine intermediate complex, which reacts with the oxidant by an inner-sphere mechanism leading to decomposition of the complex in the rate-determining step. The final oxidation products of histidine were identified as the corresponding aldehyde (2-imidazole acetaldehyde), ammonium ion and carbon dioxide. The mechanisms of these reactions have been proposed and the appropriate rate laws are deduced
Research Abstract
Research Date
Research File
Research Journal
Transition Metal Chemistry
Research Member
Research Publisher
Springer
Research Rank
2
Research Vol
40
Research Year
2015
Research Pages
287–295