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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)


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.


  1. Kaushik R.D., Arya R.K. and Kumar S., Periodate oxidation of aromatic amines - Kinetics and mechanism of oxidation of N ethylaniline in acetone water medium, Asian. J. Chem., 12(4), 1229 (2000)
  2. Panigrahi G.P. and Mishra P.K., Kinetics and Mechanism of Os(VIII) Catalyzed Oxidation of Cyclohexanone by Alkaline Periodate, Indian. J. Chem. 16A(9), 762 (1978)
  3. Katsuki T., Mn-salen catalyst, competitor of enzymes, for asymmetric epoxidation, J. Mol.Catal. A: Chem.,113, 87 (1996)
  4. Groves J.T. and Nemo T.E., Epoxidation reactions catalyzed by iron porphyrins, Oxygen transfer from iodosylbenzene, J. Am. Chem. Soc.,105, 5786 (1983)
  5. Sugimoto H., Tung H.C. and Sawyer D.T., The formation, characterization, and reactivity of the oxene adduct of [tetrakis(2,6-dichlorophenyl) porphinato] iron (III) perchlorate in acetonitrile, Model for the reactive intermediate of cytochrome P-450, J. Am. Chem. Soc., 110,2465 (1988)
  6. Mohajer D. and Tangestanninejad S., Efficient olefin epoxidation with tetrabutylammonium periodate catalyzed by manganese porphyrin in the presence of imidazole, Tetrahedron Lett., 6, 945 (1994)
  7. Curci R., Advances in Oxygenated Processes, edited by A.L. Baumstark (Greenwich Press) (1990)
  8. Ballistreri F.P., Thmaselli G.A., Toscano R.M., Bonchio M., Conte V., and Di Fura F., The relative reactivity of thioethers and sulfoxides toward oxygen transfer reagents: the case of dioxiranes, Tetrahedron Lett.,35, 8041 (1994)
  9. Mirkhani V., Tangestaninejad S., Moghadam M. and Moghbel M., Cytochrome P-450 dependent monooxygenases model system: rapid and efficient oxidation of primary aromatic amines to azo derivatives with sodium periodate catalyzed by manganese(III) Schiff base complexes, Bioorg. Med. Chem., 12, 4673 (2004)
  10. Mohajer D. and Tangestaninejad S., Efficient catalytic epoxidation of alkenes by a manganese porphyrin and periodate in the presence of imidazole, J. Chem. Soc. Chem. Commun., 240 (1993)
  11. Johnson C.R. and McCants D., The Stereochemistry of Oxidation at Sulfur. Oxidation of 4-Substituted Thianes to Sulfoxides, J. Am. Chem. Soc. 87, 1109 (1965)
  12. Ruff F. and Kucsman A., Mechanism of the oxidation of sulphides with sodium periodate, J. Chem. Soc. Perkin Trans., 2, 683 (1985)
  13. Chellamani A. and Harikengaram S., Kinetics and mechanism of (salen)MnIII-catalysed oxidation of organic sulfides with sodium hypochlorite, J. Phys. Org. Chem.,16,589 (2003)
  14. Srinivasan K., Michaud P. and Kochi J.K., Epoxidation of olefins with cationic (salen) manganese (III) complexes, The modulation of catalytic activity by substituents, J. Am. Chem. Soc.,108, 2309 (1986)
  15. Meunier B., De carvalho M.E., Bortolini O. and Momentea M., Proximal effect of the nitrogen ligands in the catalytic epoxidation of olefins by the sodium hypochlorite/manganese(III) porphyrin system, Inorg. Chem.,27, 161 (1988)
  16. Srinivasan C., Chellamani A. and Rajagopal S., Mechanism of the oxidation of alkyl aryl and diphenyl sulfides by chromium(VI), J. Org. Chem.50, 1201 (1985)
  17. Baciocchi E., Intini D., Piermattei A., Roh C. and Ruzziconi R., Product and Kinetic Study of the Oxidation of Thioethers by Cerium(IV) Ammonium Nitrate in Acetic Acid, Gazz. Chim. Ital., 119, 649 (1989)
  18. Balakumar S., Thanesekaran P., Rajagopal S. and Ramaraj R., Electron transfer reactions of iron (III) - polypyridyl complexes with organic sulphides, Tetrahedron.,51, 4801 (1995)
  19. Miller A.E., Bischoff J.J., Bizub C., Luminnoso P. and Smiley S., Electronic and Steric Effects in Oxidations by Isoalloxazine 4a-Hydroperoxides, J. Am. Chem. Soc.,108,7773 (1986)
  20. Oae S., Watanabe Y. and Fujimori K., Biomimetic oxidation of organic sulfides with TPPFe(III)Cl/imidazole/ hydrogen peroxide, Tetrahedron Lett., 23, 1189 (1982)
  21. March J., Advanced Organic Chemistry (4th edn), Wiley : New York, 251 (1992)
  22. Vyas V.K., Jalani N., Kothari S. and Banerji K.K., Kinetics and mechanism of the oxidation of organic sulfides by pyridinium hydrobromide perbromide, J. Chem. Res., 370 (1996)
  23. Srinivasan C., Rajagopal S. and Chellamani A., Mechanism of picolinic-acid-catalysed chromium(VI) oxidation of alkyl aryl and diphenyl sulphides, J. Chem. Soc. Perkin Trans., 2,1839 (1990)
  24. Sevvel R., Rajagopal S., Srinivisan C., Alhaji N.M.I. and Chellamani A., Mechanism of Selective Oxidation of Organic Sulfides with Oxo(salen)chromium(V) Complexes, J. Org. Chem.,65, 3334 (2000)
  25. Erdik E. and Eroglu F., Kinetics and mechanism of the C-S coupling reactions of aryl Grignard reagents with aryl arenesulfonates, Cent. Eur. J. Chem.,6, 237 (2008)
  26. Koh H.J., Kang S.J. and Kevil D.N., Correlation of the Rates of Solvolysis of Diphenylthiophosphinyl Chloride Using an Extended form of the Grunwald-Winstein Equation, Bull. Korean. Chem. Soc.,29, 1927 (2008)
  27. Ganesan T.K., Rajagopal S. and Bharathy J.B., Comparative Study of Chromium(V) and Chromium(VI) Oxidation of Dialkyl Sulfides, Tetrahedron., 56, 5885 (2000)
  28. Diwya Pushpa I. and Ramachandrppa R., Oxidation of Tranexamic Acid by Bromamine T in HCl Medium Catalyzed by RuCl: A Kinetic and Mechanistic Approach, Res.J.Chem.Sci. 2(7), 15 (2012)
  29. Kumar G.M. and Rajput Surendra K., Uncatalysed Oxidation of Dextrose by Cerium(IV) in Aqueous Acidic Medium-A Kinetic and Mechanistic Study, Res.J.Chem.Sci., 2(11), 60 (2012)