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Kinetics and Mechanism of (salen)MnIII Catalyzed Oxidation of Aryl phenyl Sulfides with Sodium Metaperiodate

Author Affiliations

  • 1Department of Chemistry, Manonmaniam Sundaranar University, Tirunelveli 627012,INDIA

Res.J.chem.sci., Volume 3, Issue (4), Pages 29-35, April,18 (2013)

Abstract

The oxidation of 4-substituted phenyl phenyl sulfides was carried out with several oxo(salen)manganese(V) complexes in MeCN/HO2 9:1. The oxidation follows an overall second-order kinetics, first-order each in sulfide and oxo(salen)manganese(V) complex. Electron-attracting substituents in the sulfide and electron-releasing substituents in salen of the oxo(salen)manganese(V) complexes reduce the rate of oxidation. A Hammett analysis of the rate constants for the oxidation of 4-substituted phenyl phenyl sulfides gives a negative value ( ρ = -2.29) indicating an electron-deficient transition state. The log k2 value observed in the oxidation of each 4-substituted phenyl phenyl sulfides by substituted oxo(salen)manganese(V) complexs also correlate with Hammett constants, giving positive value. The substituent-, acid-, and solvent-effect studies indicate direct O-atom transfer from the oxidant to the substrate in the rate-determining step.

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