Kinetic and mechanistic study of oxidation of L-methionine by Waugh-type enneamolybdomanganate(IV) in perchloric acid.
The reaction between methionine and enneamolybdomanganate(IV) in perchloric acid was carried out under pseudo-first-order conditions keeping large excess of methionine. The orders in oxidant and substrate were found to be unity and 0.91, respectively. The reaction proceeds with rapid formation of complex between the reactants followed by its decomposition in a rate determining step. The accelerating effect of hydrogen ions on the reaction is due to the formation of active hexaprotonated oxidant species. The product of the reaction was found to be methionine sulfoxide. The reaction involves direct two-electron transfer step without any free radical intervention. The effect of ionic strength, solvent polarity and the activation parameters were also in support of the mechanism proposed.
Kinetics and Catalysis Laboratory, Department of Chemistry, Shivaji University, Kolhapur 416004, India.
V M
VM
Gurame
A R
AR
Supale
Gavisiddappa S
GS
Gokavi
D002384:Catalysis; D056831:Coordination Complexes / Q000138:chemical synthesis / Q000737:chemistry*; D005609:Free Radicals / Q000032:analysis; D006863:Hydrogen-Ion Concentration; D007700:Kinetics; D008715:Methionine / Q000031:analogs & derivatives / Q000138:chemical synthesis / Q000737:chemistry*; D008958:Models, Molecular; D009994:Osmolar Concentration; D010084:Oxidation-Reduction; D010472:Perchlorates / Q000737:chemistry*; D012997:Solvents; D013054:Spectrophotometry, Atomic; D017550:Spectroscopy, Fourier Transform Infrared; D013454:Sulfoxides / Q000138:chemical synthesis
D056831:Coordination Complexes; D005609:Free Radicals; D010472:Perchlorates; D012997:Solvents; D013454:Sulfoxides; D008715:Methionine; C013111:methionine sulfoxide