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The base hydrolysis ofmer-[Co(1,5-diamino-3-azapentane)(amino acidate)X]+ (X = Cl or NO2) complexes and base hydrolysis of complexed peptides in the coordination sphere of the [Co(dien)]3+ moiety

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Summary

A variety ofmer-[Co(dien)(AA)X]+ (AA = amino acidate, dien = 1,5-diamino-3-azapentane) andmer-[Co(dien)(dipeptideOR)X]2+ complexes (X = Cl or NO2) have been prepared and characterised. Base hydrolysis of the peptide bond in the carbonyl bonded glycyl peptides has been studied at 25°C and I = 0.1 mol dm−3. The rate constants kOH for peptide bond hydrolysis fall within the 0.67–0.88 mol dm−3s−1 range. Base hydrolysis of the complexed peptide isca. 2×104 times faster than for the uncomplexed peptide ligand at 25 °C. The base hydrolysis of the chloro- and nitro-ligands in these complexes has also been studied. Very rapid hydrolysis occurs if the dien ligand adopts amer-configuration and the reactions are 102–104 times faster than for analogous complexes where the dien ligand adopts afac-configuration. These results are in agreement with Tobe's criteria for rapid base hydrolysis in cobalt(III) complexes.

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Abbreviations

dien:

1,5-diamino-3-azapentane

dpt:

1,7-diamino-4-azaheptane

glyO:

glycinate

glyOH:

glycine

glyOR:

glycine ester

glyNH2 :

glycine amide

glyglyO:

glycylglycinate

glyglyOR:

glycylglycine ester

glyglyglyOH:

triglycine

α-alaO:

α-alaninate

References

  1. R. W. Hay,Bio-Inorganic Chemistry, Ellis Horwood, Chichester, 1984.

    Google Scholar 

  2. W. N. Lipscombe,Chem. Soc. Rev., 1, 319 (1972).

    Google Scholar 

  3. W. N. Lipscombe,Tetrahedron, 30, 1725 (1974).

    Google Scholar 

  4. R. W. Hay and P. J. Morris in H. Sigel (Ed.),Metal Ions in Biological Systems, Vol. 5, Marcel Dekker, New York, N.Y., 1976.

    Google Scholar 

  5. D. A. Buckingham in A. W. Addison, W. R. Cullen, D. Dolphin and B. R. James (Eds.),Biological Aspects of Inorganic Chemistry, Wiley-Interscience, New York, N.Y. 1977.

    Google Scholar 

  6. N. E. Dixon and A. M. Sargeson inZinc Enzymes, T. G. Spiro (Ed.), Wiley, New York, N.Y., 1983.

    Google Scholar 

  7. Y. Wu and D. H. Busch,J. Am. Chem. Soc., 94, 4115 (1972).

    Google Scholar 

  8. K. Ohkawa, J. Fujita and Y. Shimura,Bull. Chem. Soc. Jpn., 45, 161 (1972).

    Google Scholar 

  9. A. Y. Girgis and J. I. Legg,J. Am. Chem. Soc., 94, 8420 (1972).

    Google Scholar 

  10. L. F. Vilas-Boas,PhD thesis, University of Kent at Canterbury, U.K., 1974.

    Google Scholar 

  11. Gillard and Philipps have reported that attempted preparations of [Co(dien)(glyglyglyO)]+ gave [Co(dien)(glyglyO)+, the latter being formed by hydrolysis of the tripeptide. R. D. Gillard and D. A. Phipps,Chem. Comm., 800 (1972).

  12. R. A. Henderson and M. L. Tobe,Inorg. Chem., 16, 2576 (1977).

    Google Scholar 

  13. R. W. Hay and D. P. Piplani,Kemiai Közlémenyek, 48, 47 (1977).

    Google Scholar 

  14. S. H. Caldwell and D. A. House,J. Inorg. Nucl. Chem., 31, 811 (1969).

    Google Scholar 

  15. M. D. Alexander and D. H. Busch,Inorg. Chem., 5, 1590 (1966).

    Google Scholar 

  16. R. A. Robinson and R. H. Stokes,Electrolyte Solutions, 2nd edit., Butterworths, London, 1965.

    Google Scholar 

  17. C. W. Davies,J. Chem. Soc., 2093 (1938).

  18. S. Yamaguchi and S. Ooi, quoted in ref. 8.

    Google Scholar 

  19. R. W. Hay and K. B. Nolan,J. Inorg. Nucl. Chem., 38, 2118 (1976).

    Google Scholar 

  20. L. S. Doug and D. A. House,Inorg. Chem. 4 1522 (1965).

    Google Scholar 

  21. J. P. Collman and E. Kimura,J. Am. Chem. Soc., 89, 6096 (1967).

    Google Scholar 

  22. D. A. Buckingham, C. E. Davis, D. M. Foster and A. M. Sargeson,J. Am. Chem. Soc., 92, 5571 (1970).

    Google Scholar 

  23. R. W. Hay and P. J. Morris,Chem. Comm., 1208 (1969).

  24. D. A. Buckingham, J. MacB. Harrowfield and A. M. Sargeson,J. Am. Chem. Soc., 96, 1726 (1974).

    Google Scholar 

  25. R. W. Hay and R. Bembi,Inorg. Chim. Acta, 64, L199 (1982).

    Google Scholar 

  26. A. Albert and E. P. Sargent,Ionisation Constants of Acids and Bases, Methuen and Co. Ltd., London, 1962.

    Google Scholar 

  27. I. J. Grant and R. W. Hay,Aus. J. Chem., 19, 1189 (1965).

    Google Scholar 

  28. M. M. Jones, T. J. Cook and S. Brammer,J. Inorg. Nucl. Chem., 28, 1265 (1966).

    Google Scholar 

  29. D. A. Buckingham, G. S. Binney, C. R. Clark, B. Garnham and J. Simpson,Inorg. Chem., 24, 135 (1985).

    Google Scholar 

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Authors and Affiliations

  1. Chemistry Department, University of Stirling, FK9 4LA, Stirling, UK

    Robert W. Hay, Valerie M. C. Reid & Dharam P. Piplani

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  1. Robert W. Hay
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  2. Valerie M. C. Reid
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  3. Dharam P. Piplani
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Hay, R.W., Reid, V.M.C. & Piplani, D.P. The base hydrolysis ofmer-[Co(1,5-diamino-3-azapentane)(amino acidate)X]+ (X = Cl or NO2) complexes and base hydrolysis of complexed peptides in the coordination sphere of the [Co(dien)]3+ moiety. Transition Met Chem 11, 302–307 (1986). https://doi.org/10.1007/BF00620652

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  • DOI: https://doi.org/10.1007/BF00620652

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