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Spectral and Mechanistic Investigation of the Osmium(VIII) Catalyzed Oxidation of Diclofenac Sodium by the Copper(III) Periodate Complex in Aqueous Alkaline Medium

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Abstract

The kinetics of the osmium(VIII) (Os(VIII)) catalyzed oxidation of diclofenac sodium (DFS) by diperiodatocuprate(III) (DPC) in aqueous alkaline medium has been studied spectrophotometrically at a constant ionic strength of 1.0 mol⋅dm−3. The reaction showed first order kinetics in [Os(VIII)] and [DPC] and less than unit order with respect to [DFS] and [alkali]. The rate decreased with increase in [periodate]. The reaction between DFS and DPC in alkaline medium exhibits 1:2 [DFS]:[DPC] stoichiometry. However, the order in [DFS] and [OH−] changes from first order to zero order as their concentration increases. Changes in the ionic strength and dielectric constant did not affect the rate of reaction. The oxidation products were identified by LC-ESI-MS, NMR, and IR spectroscopic studies. A possible mechanism is proposed. The reaction constants involved in the different steps of the mechanism were calculated. The catalytic constant (K C) was also calculated for Os(VIII) catalysis at the studied temperatures. From plots of log 10 K C versus 1/T, values of activation parameters have been evaluated with respect to the catalytic reaction. The activation parameters with respect to the slow step of the mechanism were computed and discussed, and thermodynamic quantities were also determined. The active osmium(VIII) and copper(III) periodate species have been identified.

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References

  1. Niu, W., Zhu, Y., Hu, K., Tong, C., Yang, H.: Kinetics of oxidation of SCN− by diperiodatocuprate(III) (DPC) in alkaline medium. Int. J. Chem. Kinet. 28, 899–904 (1996)

    Article  CAS  Google Scholar 

  2. Suresh, D.K., Nandibewoor, S.T.: A kinetic and mechanistic study on the oxidation of isoniazid drug by alkaline diperiodatocuprate(III)—A free radical intervention. Trans. Met. Chem. 31, 1034–1039 (2006)

    Article  Google Scholar 

  3. Chimatadar, S.A., Kini, A.K., Nandibewoor, S.T.: Free radical intervention in the oxidation of sulfanilic acid by alkaline diperiodatocuprate(III) complex: a kinetic and mechanistic approach. Int. J. Chem. Kinet. 77(A), 117–121 (2007)

    Google Scholar 

  4. Ramreddy, M.G., Sethuram, B., Navaneeth Rao, T.: Effect of copper(II) on kinetics and mechanism of silver(I) catalysed oxidation of some amino acids by peroxydisulfate ion in aqueous medium. Indian J. Chem. 16A, 313–316 (1978)

    Google Scholar 

  5. Karlin, K.D., Gultneh, Y., Lipard, S.J. (eds.): Progress in Inorganic Chemistry, vol. 25, p. 220. Wiley, New York (1997)

    Google Scholar 

  6. Tolman, W.B.: Making and breaking the dioxygen O–O bond: new insights from studies of synthetic copper complexes. Acc. Chem. Res. 30, 227–237 (1997)

    Article  CAS  Google Scholar 

  7. Kitajima, N., Moro-oka, Y.: Copper-dioxygen complexes inorganic and bioinorganic perspectives. Chem. Rev. 94, 737–757 (1994)

    Article  CAS  Google Scholar 

  8. Karlin, K.D., Kaderli, S.A., Zuberbuhler, D.: Kinetics and thermodynamics of copper(I)/dioxygen interaction. Acc. Chem. Res. 30, 139–147 (1997)

    Article  CAS  Google Scholar 

  9. Piere, J.L.: One electron at a time oxidations and enzymatic paradigms: from metallic to non-metallic redox centers. Chem. Soc. Rev. 29, 251–257 (2000)

    Article  Google Scholar 

  10. Peisach, J., Alsen, P., Blumberg, W.E.: The Biochemistry of Copper. Academic Press, New York (1966)

    Google Scholar 

  11. Iliescu, T., Baia, M., Miclaus, V.: A Raman spectroscopic study of the diclofenac sodium–β-cyclodextrin interaction. Eur. J. Pharm. Sci. 22, 487–495 (2004)

    Article  CAS  Google Scholar 

  12. Gostick, N., James, I.G., Khong, T.K., Roy, P., Shepherd, P.R., Miller, A.J.: Controlled-release indomethacin and sustained-release diclofenac sodium in the treatment of osteoarthritis: a comparative controlled clinical trial in general practice. Curr. Med. Res. Opin. 12, 135–142 (1990)

    CAS  Google Scholar 

  13. Crowley, B., Hamill, J.J., Lyndon, S., Mckellican, J.K., Williams, P., Miller, A.J.: Controlled-release indomethacin and sustained-release diclofenac sodium in the treatment of rheumatoid arthritis: a comparative controlled clinical trial. Curr. Med. Res. Opin. 12, 143–150 (1990)

    CAS  Google Scholar 

  14. Das, A.K.: Kinetic and mechanistic aspects of metal ion catalysis in cerium(IV) oxidation. Coord. Chem. Rev. 213, 307–325 (2001)

    Article  CAS  Google Scholar 

  15. Agrawal, M.C., Upadhyay, S.K.: Osmium as catalyst in some redox reactions. J. Sci. Ind. Res. 42, 508–517 (1983)

    CAS  Google Scholar 

  16. Hugar, G.H., Nandibewoor, S.T.: Kinetics of osmium(VIII) catalysis of periodate oxidation of dimethylformamide in aqueous alkaline medium. Transit. Met. Chem. 19, 215–217 (1994)

    Article  CAS  Google Scholar 

  17. Veerasomaiah, P., Reddy, K.B., Sethuram, B., Navaneeth Rao, T.: Role of osmium tetroxide in oxidation of 2-propanol in presence and absence of different one and two equivalent oxidants in aqueous alkaline medium. Indian J. Chem. 26A, 402–406 (1987)

    Google Scholar 

  18. EI-Tantawy, Y.A., Abu-Shady, A.I., Ezzat, I.T.: The mechanism of Os(VIII)-catalyzed Ce(IV–As(III) reaction. J. Inorg. Nucl. Chem. 40, 1683–1684 (1978)

    Article  Google Scholar 

  19. Sinha, B.P., Mathur, H.P.: Kinetics and mechanism of the oxidation of thallium(I) by cerium(IV) catalysed by Os(VIII) in perchloric acid medium. J. Inorg. Nucl. Chem. 246, 1673–1679 (1971)

    Article  Google Scholar 

  20. Sirsalmath, K.T., Hiremath, C.V., Nandibewoor, S.T.: Kinetic, mechanistic and spectral investigations of ruthenium(III)/osmium(VIII) catalysed oxidation of paracetamol by alkaline diperiodatoargentate(III) (stopped flow technique). Appl. Catal. 305, 79–89 (2006)

    Article  CAS  Google Scholar 

  21. Patil, R.H., Naik, P.N., Nandibewoor, S.T.: Mechanistic investigation of oxidation of diclofenac sodium by diperiodatocuprate(III) complex in aqueous alkaline medium. Prog. React. Kinet. Mech. 34, 329–346 (2009)

    Article  Google Scholar 

  22. Jaiswal, P.K., Yadava, K.L.: Determination of sugars and organic acids with periodato complex of Cu(III). Indian J. Chem. 11, 837–839 (1973)

    CAS  Google Scholar 

  23. Murthy, C.P., Sethuram, B., Navaneeth Rao, T.: Kinetics of oxidation of some alcohols by diperiodatocuprate(III) in alkaline medium. Z. Phys. Chem. 262, 336–340 (1981)

    CAS  Google Scholar 

  24. Jeffery, G.H., Bassett, J., Mendham, J., Denney, R.C.: Vogel’s Textbook of Quantitative Chemical Analysis, 5th edn., p. 455. ELBS, Longman, Essex (1996)

    Google Scholar 

  25. Panigrahi, G.P., Misro, P.K.: Kinetics and mechanism of oxidation of Os(VIII) catalysed oxidation of unsaturated acids by sodium periodate. Indian J. Chem. 16A, 201–204 (1978)

    CAS  Google Scholar 

  26. Kolthoff, I.M., Meehan, E.J., Carr, E.M.: Mechanism of initiation of emulsion polymerization by persulfate. J. Am. Chem. Soc. 75, 1439–1441 (1953)

    Article  CAS  Google Scholar 

  27. Bhattacharya, S., Banerjee, P.: Kinetic studies on the electron transfer between azide and nickel(IV) oxime imine complexes in aqueous solution. Bull. Chem. Soc. Jpn. 69, 3475–3482 (1996)

    Article  CAS  Google Scholar 

  28. Moelwyn-Hughes, E.A.: Kinetics of Reaction in Solutions. Oxford University Press, London (1947)

    Google Scholar 

  29. Reddy, K.B., Sethuram, B., Navaneeth Rao, T.: Photon cross sections in copper, platinum and gold at 81 keV. Z. Phys. Chem. 268, 706–710 (1987)

    CAS  Google Scholar 

  30. Kiran, T.S., Hiremath, C.V., Nandibewoor, S.T.: Kinetic, mechanistic and spectral investigations of ruthenium(III)/osmium(VIII) catalysed oxidation of paracetamol by alkaline diperiodatoargentate(III) (stopped flow technique). Appl. Catal. A. Gen. 305, 79–89 (2006)

    Article  Google Scholar 

  31. Sethuram, B.: Some Aspects of Electron Transfer Reactions Involving Organic Molecules. Allied Publishers, New Delhi (2000)

    Google Scholar 

  32. Reddy, K.B., Sethuram, B., Navaneeth Rao, T.: Kinetics of oxidative deamination and decarboxylation of some amino acids by diperiodatocuprate(III) in alkaline medium. Indian J. Chem. 20A, 395–397 (1981)

    CAS  Google Scholar 

  33. Murthy, C.P., Sethuram, B., Reddy, K.B., Navaneeth Rao, T.: Kinetics of oxidation of benzaldehydes by copper(III) in t-butanol water medium. Indian J. Chem. 23A, 593–595 (1984)

    Google Scholar 

  34. Kamble, D.L., Nandibewoor, S.T.: Osmium(VIII)/ruthenium(III) catalysis of periodate oxidation of acetaldehyde in aqueous alkaline medium. J. Phys. Org. Chem. 11, 171–176 (1998)

    Article  CAS  Google Scholar 

  35. Lister, M.W.: The stability of some complexes of trivalent copper. Can. J. Chem. 31, 638–652 (1953)

    Article  CAS  Google Scholar 

  36. Kiran, T.S., Hiremath, D.C., Nandibewoor, S.T.: Oxidation of L-lysine by diperiodatocuprate(III) in aqueous alkaline medium by stopped flow technique. Russ. J. Phys. Chem. 81, 2070–2077 (2007)

    Article  CAS  Google Scholar 

  37. Weissberger, A., Lewis, E.S. (eds.): Investigations of rates and mechanism of reactions. In: Techniques of Chemistry. Wiley, New York (1974)

  38. Walling, C.: Free Radicals in Solution. Academic Press, New York (1957)

    Google Scholar 

  39. Farokhi, S.A., Nandibewoor, S.T.: Kinetic, mechanistic and spectral studies for the oxidation of sulfanilic acid by alkaline hexacyanoferrate(III). Tetrahedron 59, 7595–7602 (2003)

    Article  CAS  Google Scholar 

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  1. P.G. Department of Studies in Chemistry, Karnatak University, Dharwad, 580003, India

    Shekappa D. Lamani, Praveen N. Naik & Sharanappa T. Nandibewoor

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  1. Shekappa D. Lamani
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Correspondence to Sharanappa T. Nandibewoor.

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Lamani, S.D., Naik, P.N. & Nandibewoor, S.T. Spectral and Mechanistic Investigation of the Osmium(VIII) Catalyzed Oxidation of Diclofenac Sodium by the Copper(III) Periodate Complex in Aqueous Alkaline Medium. J Solution Chem 39, 1291–1310 (2010). https://doi.org/10.1007/s10953-010-9587-9

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