Oxidation of 3-Hydroxy-6-methyl-2-pyridinemethanol by Chromium(VI) in Acidic Aqueous Media ; Kinetic and EPR Studies

• Autorzy: Kita, E. , Wrzeszcz, G.
• Języki publikacji: EN

Abstrakty

EN

Kinetics of oxidation of 3-hydroxy-6-methyl-2-pyridinemethanol (hmpol) by CrVI at HClO4 was studied under the pseudo-first-order conditions. The hmpol oxidation products were the appropriate aldehyde (hmpal) and acid (hmpac) coordinated to the chromium( III). The linear dependence of the pseudo-first-order rate constant (kobs) on [hmpol] at 1.0 and 2.0 M HClO4 and a parabolic dependence of kobs on [H+] were established. The apparent activation parameters were determined from the second-order rate constants at 1.0MHClO4. The presence of the CrII and CrIV intermediates was deduced, based on rate retardation effect caused by O2 and MnII respectively, whereas the presence of CrV was established by EPR. Some correlations between the structure and stability of intermediate chromium(V) complexes have been discussed from EPR spectra, recorded during the redox process.

Słowa kluczowe

EN

kinetics; oxidation of 3-hydroxy-6-methyl-2-pyridinemethanol; reduction of chromium(VI); EPR of chromium(V)

• Czasopismo: Polish Journal of Chemistry
• Rocznik: 2003
• Tom: Vol. 77 / nr 3
• Strony: 355-364
• Opis fizyczny: Bibliogr. 23 poz., rys.

Twórcy

autor

Kita, E.

• Department of Chemistry, N. Copernicus University, 87-100 Toruń, Poland

autor

Wrzeszcz, G.

• Department of Chemistry, N. Copernicus University, 87-100 Toruń, Poland

Bibliografia

• 1. Kita E., Kita P. and Wiśniewska J., Polish J. Chem., 70, 354 (1996).
• 2. Kita E. and Uścińska G., Transition Met. Chem., 28 (2003) in press.
• 3. Kita E. and Uścińska G., Transition Met. Chem., 28 (2003) in press.
• 4. Nakamoto K. and Martell A.E., J. Am. Chem. Soc., 81, 5857 (1959).
• 5. Duling D.R., J. Magn. Reson., B104, 105 (1994).
• 6. Nakamoto K. and Martell A.E., J. Am. Chem. Soc., 81, 5863 (1959).
• 7. Scott S.L., Bakac A. and Espenson J.H., J. Am. Chem. Soc., 114, 4205 (1992).
• 8. Perez-Benito J.F. and Arias C., Can. J. Chem., 71, 649 (1993).
• 9. Bakac A., Prog. Inorg. Chem., 43,267 (1995).
• 10. Bakac A. and Espenson J.H., Acc. Chem Res., 26, 519 (1993).
• 11. Sen Gupta K.K., Samanta T. and Basu S.N., Tetrahedron, 42, 681 (1986).
• 12. Sen Gupta K.K., Dey S., Sen Gupta S., Adhikari M. and Banerjee A., Tetrahedron, 46, 2431 (1990).
• 13. Mitewa M. and Bontchev P.R., Coord. Chem. Rev., 61, 241 (1985).
• 14. Krumpolc M., Deboer B.G. and Roćek J., J. Am. Chem. Soc., 100, 145 (1978).
• 15. Farrell R.P. andLayP.A., Comm. Inorg. Chem., 13, 135 (1992).
• 16. Bose R.N., Moghaddas S. and Gelerinter E., Inorg. Chem., 31, 1987 (1992).
• 17. Mitewa M., Malinovski A., Bontchev P.R. and Kabassanov K, Inorg. Chim. Acta, 8, 17 (1974).
• 18. Headlam H.A. and Lay P.A., Inorg. Chem., 40, 78 (2001).
• 19. Farrell R.P., Lay P.A., Levina A., Maxwell I.A., Bramley R., Brumby S. and Ji J.-Y., Inorg. Chem., 37,3159(1998).
• 20. Barr-David G., Charara M., Codd R., Farrell R.P., Irwin J.A., Lay P.A., Bramley R., Brumby S, Ji J.-Y. and Hanson G.R., J. Chem. Soc., Farad. Trans., 91, 1207 (1995).
• 21. Roćek J. and Ng C.-S., J. Org. Chem., 38, 3348 (1973).
• 22. Wiberg K.B., Oxidation in Organic Chemistry, Academic Press, NY, 1993.
• 23. Perez-Benito J.F. and Arias C., An. Quim., 89, 636 (1993).