The Kinetics of the Oxidation of Lysine by μ-Peroxo-Bridged Binuclear Cobalt (III) Complex of Succinimide in Aqueous Hydrochloric Acid Medium

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Abstract

Kinetics of oxidation of Lysine (Lys) and mechanisms by μ-peroxo bis[bis(ethylenediamine)succinimidato-dicobalt(III)]dinitratedihydrate; [LCo(μ-O2)CoL](NO3)2.2H2O (L = suc(en)2), hereafter the complex, was investigated at 420 nm wavelength of maximum absorption of the complex under the conditions hydrogen ions concentration = 1.8 × 10-2 mol dm-3, temperature = 24 ± 1 °C, [LCo(μ-O2)CoL2+] = 1.4 × 10-4 mol dm-3 and ionic strength = 0.5 mol dm-3. First order in [LCo(μ- O2)CoL2+] and [Lys] were obtained but inverse first order in [H+]. The proposed overall rate equation is as shown:

Rate of the reaction decreases when hydrogen ions concentration increase and exhibited converse effect with increase in concentration of ionic strength from 0.1 - 1.3 mol dm-3. Added cations and anions affected the reaction rate and the Michaelis-Menten plot passed through the origin indicating no absence of intermediate complex in the electron transfer processes. Putting all the results obtained together, the most probable reaction mechanism is in favour of outer-sphere and an appropriate rate law is established using steady state approximation.

References

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  • Iyun J. Ukoha P. 1999 Kinetics and mechanism of oxidation of 1 3- dihydroxybenzene by trioxoiodate (V) ion in aqueous perchloric acid medium.

  • Gouda N.M.M. Mahadevappab D.S. Rangappa K.S; Thimmegouda B. 1986 Oxidimetric determination of amino acids and their metal complexes with organic monochloramies International Journal of Chemical Kinetic 2 165-178.

  • Mohanty B. Behera J. Acharya S. Mohanty P. Pantaik A. 2013 Metal ion catalyzed oxidation of L-lysine by alkaline permanganate Ion-A kinetic and mechanistic approach. Chem Sci Trans 2 51-60.

  • Orhan B. 2009 Synthesis and structural characterization of a novel peroxo bridged binuclear cobalt(III) complex of succinimide showing three varieties of hydrogen bonding interaction. Journal of Chemical Science. 121(3) 267-273.

  • Roberts J.D. Caserio M.C. 1977 Basic principles of organic chemistry. WA Benjamin Inc.

  • Wilkins R.G. 2002 Kinetics and mechanism of reactions of transition metal complexes 2nd Ed. Wiley-VCH & Co

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  • Devra V. 2005 Kinetics and mechanism of silver (I) catalyzed oxidation of alanine by cerium (IV) in perchloric acid medium. Journal of the Indian Chemical Society 82 290-294.

  • Elias H. 1992 RG Wilkins: Kinetics and Mechanism of Reactions of Transition Metal Complexes 2nd Thoroughly Revised Edition. VCH Weinheim 1991. ISBN 3-527-28389-7. 482 Seiten. Preis (Softcover): DM 68.00. Berichte der Bunsengesellschaft für physikalische Chemie 96 638-639.

  • Goel A. Sharma R. 2012 A kinetic and mechanistic study on the oxidation of arginine and lysine by hexacyanoferrate (III) catalysed by iridium (III) in aqueous alkaline medium. Journal of Chemical Engineering and Materials Science 3 1-6.

  • Goel A. Sharma S. 2010 Mechanistic study of the oxidation of lphenylalanine by hexacyanoferrate (III) catalyzed by iridium (III) in aqueous alkaline medium. Transition Metal Chemistry 35 549-554.

  • Goel A. Verma G. Singh H. 2002 Kinetics and mechanism of iridium (III) chloride catalyzed oxidation of ethylene glycol and methyl glycol by hexacyanoferrate (III) in aqueous alkalinemedium. Journal of the Indian Chemical Society 79 665-667.

  • Gowda N.M.M. Rangappa K.S. Mahadevappa D.S. 1986 Oxidimetric determination of amino acids and their metal complexes with organic monochloramines. Analyst 111 1423-1429.

  • Gupta K. Gupta Y. 1984 Hydrogen-Ion dependence of Reaction Rates and mechanism. J. Chem. Educ 61 972.

  • Harihar A. Kembhavi M. Nandibewoor S. 2000 Kinetics of oxidative degradation of L (+) lysine by alkaline permanganate-A mechanistic approach.

  • Hosamani R. Nandibewoor S. 2009 Mechanistic study of ruthenium (III) catalysed oxidation of L-lysine by diperiodatoargentate (III) in aqueous alkaline medium. Journal of chemical sciences 121 275-281.

  • Iyun J. Ayoko G. Lawal H. 1992 The Stoichiometry And Kinetics Of Oxidation Of 1 4-Benzenediol By Diaquotetrakis (2 2'-Bipyridine)-Mu-Oxodiruthenium (Iii) Cation in Perchlorate Medium. Indian Journal Of Chemistry Section A-Inorganic Bio-Inorganic Physical Theoretical & Analytical Chemistry 31 943-946.

  • Iyun J. Ukoha P. 1999 Kinetics and mechanism of oxidation of 1 3- dihydroxybenzene by trioxoiodate (V) ion in aqueous perchloric acid medium.

  • Gouda N.M.M. Mahadevappab D.S. Rangappa K.S; Thimmegouda B. 1986 Oxidimetric determination of amino acids and their metal complexes with organic monochloramies International Journal of Chemical Kinetic 2 165-178.

  • Mohanty B. Behera J. Acharya S. Mohanty P. Pantaik A. 2013 Metal ion catalyzed oxidation of L-lysine by alkaline permanganate Ion-A kinetic and mechanistic approach. Chem Sci Trans 2 51-60.

  • Orhan B. 2009 Synthesis and structural characterization of a novel peroxo bridged binuclear cobalt(III) complex of succinimide showing three varieties of hydrogen bonding interaction. Journal of Chemical Science. 121(3) 267-273.

  • Roberts J.D. Caserio M.C. 1977 Basic principles of organic chemistry. WA Benjamin Inc.

  • Wilkins R.G. 2002 Kinetics and mechanism of reactions of transition metal complexes 2nd Ed. Wiley-VCH & Co

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