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

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Abstract

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 fractional-first-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.

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Authors and Affiliations

  1. Chemistry Department, Faculty of Applied Sciences, Umm Al-Qura University, Makkah Al-Mukarramah, Kingdom of Saudi Arabia

    Ahmed Fawzy & Basim H. Asghar

  2. Chemistry Department, Faculty of Science, Assiut University, Assiut, Egypt

    Ahmed Fawzy

Authors
  1. Ahmed Fawzy
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  2. Basim H. Asghar
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Correspondence to Ahmed Fawzy.

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Fawzy, A., Asghar, B.H. Kinetics and mechanism of uncatalyzed and silver(I)-catalyzed oxidation of l-histidine by hexachloroplatinate(IV) in acid medium. Transition Met Chem 40, 287–295 (2015). https://doi.org/10.1007/s11243-015-9916-3

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  • DOI: https://doi.org/10.1007/s11243-015-9916-3

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