Advertisement

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

Solvent and pressure effects on the kinetics of reaction of manganese pentacarbonyl bromide with 2,2′-bipyridyl and on the charge-transfer spectrum of MnBr(bipy)(CO)3

  • 50 Accesses

  • 5 Citations

Summary

Rate laws, rate constants, and activation volumes are reported for reaction of MnBr(CO)5 with 2,2′-bipyridyl and with 1, 10-phenanthroline in methanol. The activation volume of +22cm3 mol−1 is consistent with a predominantlyD mechanism (CO loss) in this medium, but in 50% aqueous methanol both the kinetic pattern and activation volumes in the region of −20 cm3 mol−1 for the MnBr(CO)5 + bipy reaction indicate a key role for bromide dissociation. The solvatochromic behaviour of the MnBr(bipy)(CO)3 product of these reactions is compared with that of other ternaryd 6-diimine complexes, and the piezochromic behaviour of its MLCT spectrum outlined.

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

References

  1. (1)

    J. Burgess and A. J. Duffield,J. Organometal. Chem.,177, 435 (1979).

  2. (2)

    G. Schmidt, Diplomarbeit, Technische Hochschule Darmstadt, 1985.

  3. (3)

    R. van Eldik,Angew. Chem. Int. Edn.,25, 673 (1986).

  4. (4)

    H. A. Sinn, Ph.D. Thesis, Darmstadt (1966).

  5. (5)

    H. Saito, J. Fujita and K. Saito,Bull. Chem. Soc. Jpn.,41, 863 (1968).

  6. (6)

    J. Burgess,J. Organomet. Chem.,19, 218 (1969).

  7. (7)

    S. Ernst and W. Kaim,J. Am. Chem. Soc.,108, 3578 (1986); and refs. therein.

  8. (8)

    J. Bjerrum, A. W. Adamson and O. Bostrup,Acta Chem. Scand.,10, 329 (1956).

  9. (9)

    H. Bock and H. tom Dieck,Angew. Chem. Internat. Edn.,5, 520 (1966);Chem. Ber.,100, 228 (1967).

  10. (10)

    J. Burgess,Spectrochim. Acta,26A, 1369, 1957 (1970).

  11. (11)

    R. bin Ali, J. Burgess, M. Kotowski and R. van Eldik,Transition Met. Chem.,12, 230 (1987).

  12. (12)

    M. Kotowski, R. van Eldik, R. bin Ali, J. Burgess and S. Radulović,Inorg. Chim. Acta,131, 225 (1987).

  13. (13)

    M. H. Quick and R. J. Angelici,Inorg. Synth.,19, 160 (1979).

  14. (14)

    N. Hallinan, P. McArdle, J. Burgess and P. Guardado,J. Organometal. Chem.,333, 77 (1987).

  15. (15)

    R. Mews,Angew. Chem. Int. Edn.,16, 56 (1977).

  16. (16)

    See, e.g., N. G. Connelly and L. F. Dahl,J. Chem. Soc., Chem. Commun., 880 (1970); N. G. Connelly and J. D. Davies,J. Organometal. Chem.,38, 385 (1972).

  17. (17)

    M. R. Snow and F. L. Wimmer,Inorg. Chim. Acta,44, L189 (1980).

  18. (18)

    H.-T. Macholdt and H. Elias,Inorg. Chem.,23, 4315 (1984); H.-T. Macholdt and R. van Eldik,Transition Met. Chem.,10, 323 (1985).

  19. (19)

    J. Burgess and A. E. Smith,Transition Met. Chem.,12, 140 (1987).

  20. (20)

    H. Elias, H.-T. Macholdt, K. J. Wannowius, M. J. Blandamer, J. Burgess and B. Clark,Inorg. Chem.,25, 3048 (1986).

  21. (21)

    R. J. Angelici and F. Basolo,J. Am. Chem. Soc.,84, 2495 (1962); D. A. Brown, H. J. Lyons and R. T. Sane,Inorg. Chim. Acta,4, 621 (1970).

  22. (22)

    K. Dimroth, C. Reichardt, T. Siepmann and F. Bohlmann,Ann.,661, 1 (1963); C. Reichardt,Angew. Chem. Int. Edn.,4, 29 (1965).

  23. (23)

    J. Burgess and E. Pelizzetti, to be published.

  24. (24)

    F. E. Smith and I. S. Butler,Canad. J. Chem.,47, 1311 (1969).

  25. (25)

    A. D. Allen and P. F. Barrett,Canad. J. Chem.,46, 1655 (1968).

  26. (26)

    R. Gross and W. Kaim,Inorg. Chem.,25, 498 (1986).

  27. (27)

    S. Kohlmann, S. Ernst and W. Kaim,Angew. Chem. Int. Edn.,24, 684 (1985).

  28. (28)

    M. Wrighton and D. L. Morse,J. Am. Chem. Soc.,96, 998 (1974).

Download references

Author information

Additional information

Author to whom all correspondence should be directed.

Rights and permissions

Reprints and Permissions

About this article

Cite this article

Ali, R.b., Burgess, J. & Guardado, P. Solvent and pressure effects on the kinetics of reaction of manganese pentacarbonyl bromide with 2,2′-bipyridyl and on the charge-transfer spectrum of MnBr(bipy)(CO)3 . Transition Met Chem 13, 126–130 (1988). https://doi.org/10.1007/BF01087803

Download citation

Keywords

  • Methanol
  • Physical Chemistry
  • Manganese
  • Inorganic Chemistry
  • Bromide