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Kinetics and mechanism of uncatalyzed and silver(I)-catalyzed oxidation of histidine by hexachloroplatinate(IV) in acid medium

مؤلف البحث
Ahmed Fawzy, Basim H. Asghar
ملخص البحث

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

تاريخ البحث
مستند البحث
مجلة البحث
Transition Metal Chemistry
المشارك في البحث
الناشر
Springer
تصنيف البحث
2
عدد البحث
40
سنة البحث
2015
صفحات البحث
287–295