Skip to main content
Log in

Solvent effects on reactivity trends for base hydrolysis of iron(II) complexes of tridentate Schiff base imine ligands

  • Full Papers
  • Published:
Transition Metal Chemistry Aims and scope Submit manuscript

Summary

Solubilities of salts of iron(II) complexes of tridentate imine (Schiff base) ligands are reported for aqueous solution and for solutions in methanol-water mixtures. Gibbs free energies of transfer for the iron(II) complexes have been calculated, using the TPTB assumption (i.e. assuming equality of transfer parameters for Ph4P+ and Ph4B). The derived parameters demonstrate the importance both of ion size and of hydrophilic/hydrophobic character in determining ionic solvation in binary aqueous mixtures. Kinetic data are reported for reaction of these iron(II) complexes with hydroxide in methanol—water mixtures. The transfer parameters derived for the complexes are used in the analysis of the kinetic data to describe the influence of solvent composition on the initial and transition states. Differences between this TPTB-based analysis and the results of a similar analysis based on Wells's solvent-sorting approach are discussed.

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

Access this article

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Similar content being viewed by others

References

  1. T. S. Lee, I. M. Kolthoff and D. L. Leussing,J. Am. Chem. Soc.,70, 3596 (1948); D. W. Margerum and L. P. Morgenthaler,J. Am. Chem. Soc.,84, 706 (1962); M. J. Blandamer, J. Burgess and D. L. Roberts,J. Chem. Soc., Dalton Trans., 1086 (1978).

    Article  CAS  Google Scholar 

  2. J. Burgess,J. Chem. Soc. A, 955 (1967); 497 (1968).

  3. M. J. Blandamer, J. Burgess, R. I. Haines, F. M. Mekhail, and P. Askalani,J. Chem. Soc., Dalton Trans., 1001 (1978).

  4. R. D. Gillard, D. W. Knight and P. A. Williams,Transition Met. Chem.,5, 321 (1980).

    Article  CAS  Google Scholar 

  5. R. D. Gillard,Inorg. Chim. Acta,11, L21 (1974); R. D. Gillard,Coord. Chem. Rev.,50 303 (1983); N. Serpone, G. Ponterini, M. A. Jamieson, F. Bolletta and M. Maestri,Coord. Chem. Rev.,50, 209 (1983); E. C. Constable,Polyhedron,2, 551 (1983).

    Article  CAS  Google Scholar 

  6. P. Krumholz,Inorg. Chem.,4, 612 (1965).

    Article  CAS  Google Scholar 

  7. F. P. Dwyer, N. S. Gill, E. C. Gyarfas and F. Lions,J. Am. Chem. Soc.,75, 3834 (1953).

    Article  CAS  Google Scholar 

  8. R. K. Murmann and E. A. Healy,J. Am. Chem. Soc.,83, 2092 (1961).

    Article  CAS  Google Scholar 

  9. H. A. Goodwin and F. Lions,J. Am. Chem. Soc.,82, 5013 (1960).

    Article  CAS  Google Scholar 

  10. J. Burgess and R. H. Prince,J. Chem. Soc., 6061 (1965); R. Farina, R. Hogg and R. G. Wilkins,Inorg. Chem.,7, 170 (1980); J. Burgess and M. V. Twigg,J. Chem. Soc., Dalton Trans., 2032 (1974).

  11. R. D. Gillard,Coord. Chem. Rev.,16, 67 (1975); R. D. Gillard C. T. Hughes and P. A. Williams,Transition Met. Chem.,1, 51 (1976).

    Article  CAS  Google Scholar 

  12. J. Burgess and C. D. Hubbard,Comments Inorg. Chem., to be submitted.

  13. M. J. Blandamer and J. Burgess,Coord. Chem. Rev.,31, 93 (1980).

    Article  CAS  Google Scholar 

  14. M. J. Blandamer, J. Burgess, B. Clark, P. P. Duce, A. W. Hakin, N. Gosal, S. Radulović, P. Guardado, F. Sanchez, C. D. Hubbard and E. A. Abu-Gharib,J. Chem. Soc. Faraday Trans. I,82, 1471 (1986).

    Article  CAS  Google Scholar 

  15. M. J. Blandamer, J. Burgess and E. A. Abu-Gharib,Transition Met. Chem.,9, 193 (1984).

    Article  CAS  Google Scholar 

  16. J. Burgess and E. A. Abu-Gharib,Transition Met. Chem.,9, 234 (1984).

    Article  CAS  Google Scholar 

  17. E. A. Abu-Gharib, M. J. Blandamer, J. Burgess, N. Gosal, P. Guardado, F. Sanchez and C. D. Hubbard,Transition Met. Chem.,9, 306 (1984).

    Article  CAS  Google Scholar 

  18. C. Tissier,Comptes Rend.,286C, 35 (1978).

    Google Scholar 

  19. M. H. Abraham, T. Hill, H. C. Ling, R. A. Schulz and R. A. C. Watt,J. Chem. Soc., Faraday Trans. I,80, 489 (1984).

    Article  CAS  Google Scholar 

  20. J. Burgess and C. D. Hubbard,J. Chem. Soc., Chem. Commun., 1482 (1983).

  21. C. F. Wells,J. Chem. Soc., Faraday Trans. I,70, 694 (1974).

    Article  CAS  Google Scholar 

  22. J. Burgess,Mech. Inorg. Organometal. React.,1, 151 (1983).

    Google Scholar 

Download references

Author information

Authors and Affiliations

Authors

Additional information

TMC 2612

Rights and permissions

Reprints and permissions

About this article

Cite this article

El-Samahy, A.A., Abu-Gharib, EE.A., Eltaher, AE. et al. Solvent effects on reactivity trends for base hydrolysis of iron(II) complexes of tridentate Schiff base imine ligands. Transition Met. Chem. 17, 438–442 (1992). https://doi.org/10.1007/BF02910727

Download citation

  • Received:

  • Issue Date:

  • DOI: https://doi.org/10.1007/BF02910727

Keywords

Navigation