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Kinetics and mechanism of substitution of aqua ligands fromcis-diaqua-bis(bipyridyl ruthenium(II)) complex by salicylhydroxamic acid in aqueous medium

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Summary

The kinetics of substitution of aqua ligands fromcis-[Ru(bipy)2(H2O)2]2+ ion by salicylhydroxamic acid (L) in aqueous medium has been studied spectrophotometrically at different temperatures (50–65°C). The following rate law has been established in the pH range 4.0 to 5.8;

$$k_{obs} = \frac{{k_1 (k_2 + k'_2 K/[H^ + ])[L]}}{{(k_2 + k'_2 K/[H^ + ])[L] + k_{ - 1} (1 + K/[H^ + ])}}$$

where k1 is the water dissociation rate constant of the reactant complex, k−1 is the aquation rate constant, k2 is the ligand (in neutral form i.e., SHAH) capturing rate constant and k′2 is the ligand (in anionic form i.e. SHA−) capturing rate constant of the penta coordinated intermediate, [Ru(bipy)2(H2O)]2+. Activation parameters have been calculated and compared with other substitution reactions of this complex. The rate increases with the increase in pH. The k1 values decrease with the decrease of the dielectric constant of the medium. The experimental results are consistent with a dissociative mechanism.

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Authors and Affiliations

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

    Bibekananda Mahanti & Gouri De Sankar

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  1. Bibekananda Mahanti
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  2. Gouri De Sankar
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TMC 2725

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Mahanti, B., De Sankar, G. Kinetics and mechanism of substitution of aqua ligands fromcis-diaqua-bis(bipyridyl ruthenium(II)) complex by salicylhydroxamic acid in aqueous medium. Transition Met. Chem. 17, 521–524 (1992). https://doi.org/10.1007/BF02910748

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  • DOI: https://doi.org/10.1007/BF02910748

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