Advertisement

Springer Nature is making Coronavirus research free. View research | View latest news | Sign up for updates

Synthesis and mechanistic studies on the aquation of selenitoaquobis(diamine)cobalt(III) complexes

  • 29 Accesses

  • 1 Citations

Summary

The kinetics of the aquation of four selenitoaquobisdiamine)cobalt(III) complexes to their respective diaquabis-(diamine)complexes (diamine=ethylenediamine en, propylenediamine pn, dimethylethylenediamine me2en and trimethylenediamine tmd) have been carried out conductimetrically in the 25–45 °C range. All reactions exhibit simple first order kinetics, and the rates increase with increasing temperature. In aqueous solution, the complex species exist in equilibrium with their respective hydroxo species, but only the hydroxo species are involved in the aquation process. This result is also reflected in the linear Arrhenius plot. The rates are higher in a 10% alcoholic solution than in water, but then decrease with increase in the alcohol content. A Grunwald-Winstein plot of rates in methanol yields slopes of 0.18 ± 0.04, 0.27±0.03, 0.43±0.03 and 0.34±0.02 for the four amines respectively. A dissociation mechanism is proposed for the aquation of all these complexes.

This is a preview of subscription content, log in to check access.

References

  1. (1)

    D. R. Stranks and J. K. Yandall,Inorg. Chem., 9, 751 (1970).

  2. (2)

    U. Spitzer and R. van Eldik,Inorg. Chem., 21, 4008 (1982) and ref. therein.

  3. (3)

    C. G. Barraclough and R. S. Murray,J. Chem. Soc., 7047 (1965).

  4. (4)

    B. Chakravarty and P. K. Das,Transition Met. Chem., 7, 340 (1982).

  5. (5)

    R. van Eldik and G. M. Harris,Inorg. Chem., 19, 880 (1980); R. van Eldik,Inorg. Chim. Acta, 42, 49 (1980); R. van Eldik, J. von Jouanne and H. Kelm,Inorg. Chem., 21, 2818 (1982).

  6. (6)

    A. D. Fowless and D. R. Stranks,Inorg. Chem., 16, 1276 (1977).

  7. (7)

    A. D. Fowless and D. R. Stranks,Inorg. Chem., 16, 1282 (1977).

  8. (8)

    P. Ray and A. N. Ghosh,J. Indian Chem. Soc., 13, 494 (1936).

  9. (9)

    J. Bjerrum and S. E. Rasmussen,Acta Chem. Scand., 6, 1265 (1952).

  10. (10)

    R. G. Pearson, C. R. Boston and F. Basolo,J. Amer. Chem. Soc., 75, 3089 (1953).

  11. (11)

    J. Burgess and M. G. Price,J. Chem. Soc. A, 3108 (1971).

  12. (12)

    L. A. P. Kane-Maguire and G. Thomas,J. Chem. Soc. Dalton Trans., 1324 (1975).

  13. (13)

    J. Burgess,J. Chem., Soc. Dalton Trans., 825 (1973).

  14. (14)

    A. H. Fainberg and S. Weinstein,J. Amer. Chem. Soc., 78, 2770 (1956).

  15. (15)

    C. H. Langford,Inorg. Chem., 3, 228 (1964); J. Burgess,J. Chem. Soc. A, 2703 (1970).

  16. (16)

    E. Grunwald and S. Winstein,J. Amer. Chem. Soc., 70, 846 (1948).

  17. (17)

    M. S. Lehmann and F. K. Larsen,Acta Chem. Scand., 25, 3859 (1971).

  18. (18)

    S. F. Lincoln, J. Jayne and J. P. Hunt,Inorg. Chem., 8, 2267 (1968).

  19. (19)

    G. E. Walrafen,J. Chem. Phys., 46, 1870 (1967).

  20. (20)

    F. Basolo and R. G. Pearson, “Mechanisms of Inorganic Reactions”, Wiley, New York N.Y., 1967, Chapter 3.

  21. (21)

    W. Kruse and H. Taube,J. Amer. Chem. Soc., 83, 1280 (1961).

  22. (22)

    I. Bodek, G. Davies and J. H. Ferguson,Inorg. Chem., 14, 1708 (1975); I. Bodek and G. Davies,Inorg. Chem., 14, 2580 (1975).

  23. (23)

    N. S. Rowan, C. B. Storm and J. B. Hunt,Inorg. Chem., 17, 2853 (1978).

  24. (24)

    T. J. Conocchioli, G. H. Nancollas and N. Sutin,Inorg. Chem., 5, 1 (1966).

Download references

Author information

Correspondence to Biswanath Chakravarty.

Rights and permissions

Reprints and Permissions

About this article

Cite this article

Chakravarty, B., Nandi, B. Synthesis and mechanistic studies on the aquation of selenitoaquobis(diamine)cobalt(III) complexes. Transition Met Chem 10, 171–175 (1985). https://doi.org/10.1007/BF00620665

Download citation

Keywords

  • Alcohol
  • Methanol
  • Aqueous Solution
  • Cobalt
  • Catalysis