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Kinetics and mechanism of the displacement of aqua ligands from cis-diaqua-bis(biguanide)chromium(III) by pyridine-2-aldoxime in EtOH-H2O mixtures

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Summary

Kinetic and mechanistic studies of the displacement of aqua ligands from cis-[Cr(BigH)2(H2O)2]3+ (BigH = H2NC(NH)CHC(NH)NH2) by pyridine-2-aldoxime (LH) in EtOH-H2O mixtures, in the 30–45° C range, obey the following rate law over the 3.5–6.0 pH range,

$$\frac{{d[Cr(BigH)_2 (L)^{2 + } ]}}{{dt}} = \frac{{k_a K_E [Cr(BigH)_2 (H_2 O)_2^{3 + } ]_T [LH]}}{{1 + K_E [LH]}}$$

where K E is the ion pair equilibrium constant and k a is the rate constant for the interchange of the outer-sphere complex to inner-sphere complex. The anation rate constants are dependent upon pH but independent of ionic strength. Activation parameters (ΔH ≠ and ΔS ≠) have been evaluated from Eyring plots and a mechanism (I a) involving outer-sphere association of reactants followed by associate interchange of this outer-sphere complex into product is proposed.

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References

  1. D. Banerjea and S. Dutta Chaudhury, J. Inorg. Nucl. Chem., 30, 871 (1968).

    Google Scholar 

  2. S. C. Tyagi and A. Aziz Khan, J. Inorg. Nucl. Chem., 41, 1447 (1979).

    Google Scholar 

  3. T. Ramaswami and A. G. Sykes, Inorg. Chem., 15, 2885 (1976).

    Google Scholar 

  4. T. W. Kallen and R. E. Hamm, Inorg. Chem., 18, 2151 (1979).

    Google Scholar 

  5. B. K. Niogy and G. S. De, Indian J. Chem., 24A, 208 (1985).

    Google Scholar 

  6. H. G. Mitra Mustafy and G. S. De, Proc. Ind. Acad. Sci. (Chem. Sci.), 98, 255 (1987).

    Google Scholar 

  7. P. De and G. S. De, Indian J. Chem., 30A, 1050 (1991).

    Google Scholar 

  8. H. G. Mitra Mustofy and G. S. De, Transition Met. Chem., 13, 196 (1988).

    Google Scholar 

  9. D. Banerjea and J. Roy, Z. Anog. Allg. Chem., 399, 115 (1973).

    Google Scholar 

  10. P. M. Brown and G. M. Harris, Inorg. Chem., 7, 1872 (1968).

    Google Scholar 

  11. P. Ray, J. Indian Chem. Soc., 14, 675 (1937); 15, 355 (1938).

    Google Scholar 

  12. D. Banerjea and B. Chakraborty, J. Inorg. Nucl. Chem., 26, 1233 (1964).

    Google Scholar 

  13. B. Chakraborty and A. K. Seal, Indian J. Chem., 15A, 509 (1977).

    Google Scholar 

  14. A. K. Gangopadhyay and G. S. De, Transition Met. Chem., 14, 241 (1989).

    Google Scholar 

  15. L. G. Sellin and A. E. Martel, Stability Constants of Metal Ion Complexes, Special Pub. No. 17, The Chemical Society, London, 1962.

    Google Scholar 

  16. F. Basalo and R. G. Pearson, Mechanism of Inorganic Reactions, Wiley Eastern, New Delhi, 1977, p. 154.

    Google Scholar 

  17. S. Glasstone, A Text Book of Physical Chemistry, MacMillan, London, 1977, p. 1116.

    Google Scholar 

  18. E. S. Amis and J. F. Hinton, Solvent Effect on Chemical Phenomena, Academic Press, New York, 1973, Vol. I, p. 245.

    Google Scholar 

  19. V. D. Parasyuk and L. G. Reitez, Russ. J. Inorg. Chem., 11, 329 (1966).

    Google Scholar 

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Authors and Affiliations

  1. Department of Chemistry, University of Burdwan, 713104, Burdwan, India

    Chandi C. Mukhopadhyay & Gouri S. De

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  1. Chandi C. Mukhopadhyay
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  2. Gouri S. De
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Mukhopadhyay, C.C., De, G.S. Kinetics and mechanism of the displacement of aqua ligands from cis-diaqua-bis(biguanide)chromium(III) by pyridine-2-aldoxime in EtOH-H2O mixtures. Transition Met Chem 19, 49–52 (1994). https://doi.org/10.1007/BF00166266

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  • DOI: https://doi.org/10.1007/BF00166266

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