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DOI: 10.1039/A701207A (Paper) Reference Section for: J. Chem. Soc., Dalton Trans., 1997, 1871-1876

Kinetics and mechanism of reduction of tris(acetylacetonato)manganese(III) by HONH(SO3)- and HON(SO3)22- in aqueous solution[hair space]

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Frans F. Prinsloo, Jacobus J. Pienaar and Rudi van Eldik

Abstract

The kinetics and mechanism of reduction of tris(acetylacetonato)manganese(III) [MnIII(acac)3] by HONH(SO3)- and HON(SO3)22- in aqueous solution was studied as a function of pH, [SN oxide], [acac], temperature and pressure. The oxidation of [MnII(acac)2] by one of the oxidation products of HON(SO3)22-, viz. ON(SO3)22-, was studied as a function of pH, [ON(SO3)22-], [MnII], [MnIII] and pressure. The activation parameters for the reduction by HONH(SO3)- at pH 5.2, viz ΔH[hair space]‡ = 63 ± 2 kJ mol-1, ΔS[hair space]‡ = 8 ± 6 J K-1 mol-1 and ΔV[hair space]‡ = -5.8 ± 0.5 cm3 mol-1, and for the oxidation by ON(SO3)22-, viz. ΔV[hair space]‡ = - 13.4 ± 0.7 cm3 mol-1, are discussed in terms of the nature of the electron-transfer mechanism. The kinetic data confirm the inner-sphere nature of the reactions when SN oxides react with manganese(III) complexes in general. Both the reduction and oxidation reactions are substitution-controlled redox processes. Oxidation products are generated during the reduction of the trivalent metal-ion species, which participate in the reoxidation of the metal to its trivalent state. The results are discussed with reference to data available for related reactions.

References

  1. J. Kraft and R. van Eldik, Inorg. Chem., 1989, 28, 2297; 2306; Atmos. Environ., 1989, 23, 2709 Search PubMed; K. Bal Reddy, N. Coichev and R. van Eldik, J. Chem. Soc., Chem. Commun., 1991, 481 Search PubMed; K. Bal Reddy and R. van Eldik, Atmos. Environ., 1992, 26A, 661 RSC; N. Coichev and R. van Eldik, Inorg. Chim. Acta, 1991, 185, 69 CAS; M. Dellert-Ritter and R. van Eldik, J. Chem. Soc., Dalton Trans., 1992, 1037; 1045 CrossRef CAS; N. Coichev and R. van Eldik, New J. Chem., 1994, 18, 123 Search PubMed; C. F. Botha, J. Hahn, J. J. Pienaar and R. van Eldik, Atmos. Environ., 1994, 28, 3207 Search PubMed; L. Breytenbach, W. van Pareen, J. J. Pienaar and R. van Eldik, Atmos. Environ., 1994, 28, 2451 CrossRef CAS.
  2. (a) F. F. Prinsloo, J. J. Pienaar, R. van Eldik and H. Gutberlet, J. Chem. Soc., Dalton Trans., 1994, 2373 RSC; (b) V. Lepentsiotis, F. F. Prinsloo, R. van Eldik and H. Gutberlet, J. Chem. Soc., Dalton Trans., 1996, 2135 RSC; (c) F. F. Prinsloo, J. J. Pienaar and R. van Eldik, J. Chem. Soc., Dalton Trans., 1995, 293 RSC; (d) F. F. Prinsloo, J. J. Pienaar and R. van Eldik, J. Chem. Soc., Dalton Trans., 1996, 4393 RSC.
  3. R. Banerjee, R. Das and A. K. Chakraburtty, J. Chem. Soc., Dalton Trans., 1991, 987 RSC and refs. therein.
  4. K. Yamaguchi and D. T. Sawyer, Inorg. Chem., 1985, 24, 971 CrossRef CAS.
  5. I. K. Adzamli, D. M. Davies, C. S. Stanley and A. G. Sykes, J. Am. Chem. Soc., 1981, 103, 5543 CrossRef CAS.
  6. S. Mukhopadhyay and R. Banerjee, J. Chem. Soc., Dalton Trans., 1993, 933 RSC and refs. therein.
  7. R. G. Charles and B. E. Bryant, Inorg. Synth., 1966, 7, 183.
  8. G. K. Rollefson and C. F. Oldershaw, J. Am. Chem. Soc., 1932, 54, 977 CrossRef CAS; E. Degener and F. Seel, Z. Anorg. Allg. Chem., 1956, 285, 129 CrossRef CAS; T. Haga, J. Chem. Soc., 1904, 78 Search PubMed.
  9. M. Geissler and R. van Eldik, Anal. Chem., 1992, 64, 3004 CrossRef CAS.
  10. F. F. Prinsloo, Ch. Brandt, V. Lepentsiotis, J. J. Pienaar and R. van Eldik, Inorg. Chem., 1997, 36, 119 CrossRef CAS.
  11. R. van Eldik, W. Gaede, S. Wieland, J. Kraft, M. Spitzer and D. A. Palmer, Rev. Sci. Instrum., 1993, 64, 1355 CrossRef CAS.
  12. OLIS KINFIT, OLIS Inc., Bogart, GA, 1993.
  13. G. H. Cartledge, J. Am. Chem. Soc., 1952, 74, 6015 CrossRef CAS.
  14. B. R. Stults, R. S. Marianelli and V. W. Day, Inorg. Chem., 1979, 18, 1853 CrossRef CAS.
  15. J. P. Fackler and A. Avdeef, Inorg. Chem., 1974, 13, 1864 CrossRef CAS.
  16. D. W. Thompson, J. Chem. Educ., 1971, 48, 79 CAS.
  17. B. Olbrichdeussner, W. Kaim and R. Gross, J. Organomet. Chem., 1989, 366, 155 CrossRef CAS.
  18. M. Schindehutte, P. H. van Rooyen and S. Lotz, Organometallics, 1990, 9, 293 CrossRef CAS.
  19. S. Naiditch and D. M. Yost, J. Am. Chem. Soc., 1941, 63, 2123 CrossRef CAS; D. Littlejohn, A. Wizansky and S. G. Chang, Can. J. Chem., 1989, 67, 1596 CAS.
  20. S. Aoyagui and F. Kato, J. Electroanal. Chem. Interfacial Electrochem., 1972, 38, 243 CrossRef CAS.
  21. J. P. Candlin and R. G. Wilkins, J. Am. Chem. Soc., 1965, 87, 1490 CrossRef CAS.
  22. G. Davies, Inorg. Chim. Acta, 1975, 14, L13 CrossRef CAS.
  23. S. Mukhopadhyay, S. Chaudhuri, R. Das and R. Banerjee, Can. J. Chem., 1993, 71, 2155 CAS.
  24. J. H. Murib and D. M. Ritter, J. Am. Chem. Soc., 1952, 74, 3394 CrossRef CAS.
  25. N. Löfman, Z. Anorg. Allg. Chem., 1919, 107, 241 CrossRef CAS.
  26. P. N. Balasubramanian and E. S. Gould, Inorg. Chem., 1983, 22, 1100 CrossRef.
  27. G. Raspi, A. Cinquantini and M. Cospito, Electroanal. Chem. Interfacial Electrochem., 1975, 59, 69 CrossRef CAS.
  28. V. Zang and R. van Eldik, Inorg. Chem., 1990, 29, 4462 CrossRef CAS.
  29. Y. Kurimura, Bull. Chem. Soc. Jpn., 1973, 46, 2093 CAS; Y. Kurimura, I. Sekine, E. Tsuchida and Y. Karino, Bull. Chem. Soc. Jpn., 1974, 47, 1823 CAS.
  30. M. Meier, J. Sun, J. F. Wishart and R. van Eldik, Inorg. Chem., 1996, 35, 1564 CrossRef CAS; M. Meier and R. van Eldik, Chem. Eur. J., 1997, 3, 33; J. I. Sachinidis, R. D. Richards and P. A. Tregloan, Inorg. Chem., 1996, 35, 2497 CrossRef CAS.
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