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Thermodynamics and kinetics of the formation of the supramolecular complexes bisacetato(5,10,15,20-tetraphenylporphinate)zirconium(IV) with pyridine and imidazole

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Abstract

The equilibria and rates of step reactions for the formation of the supramolecular complexes of bisacetato(5,10,15,20-tetraphenylporphinate)zirconium(IV) (AcO)2ZrTPP and bioactive bases pyridine (Py) and imidazole (Im) in toluene were studied using UV-Vis and IR spectroscopy. The step stoichiometric mechanism, including the reversible coordination of two Py molecules (K 1 = 1.8 × 108 l2/mol2), the equilibrium of the displacement of two AcO− into the second coordination sphere by increasing the concentration of the solvent polar component (K 2 = 2.4), and the coordination of the third and fourth Py molecules in a one step with the formation of [(Py)4ZrTPP]2+ · 2(AcO)− (K 3 = 2.8 × 104 l2/mol2), was verified. It was established that the spectrophotometric titration is sensible for the two-stage π-π-complexation of [(Py)4ZrTPP]2+ · 2(AcO)− with Py molecules (K 4 = 29 l/mol and K 5 = 1.8 l/mol). It was shown that the stronger base Im reacts irreversibly with (AcO)2ZrTPP. The thermodynamic and optical characteristics of (AcO)2ZrTPP required for using the complex in the detection of bioactive bases were studied.

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Authors and Affiliations

  1. Institute of Solution Chemistry, Russian Academy of Sciences, Ivanovo, 153460, Russia

    E. Yu. Tyulyaeva & T. N. Lomova

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  1. E. Yu. Tyulyaeva
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  2. T. N. Lomova
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Correspondence to T. N. Lomova.

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Original Russian Text © E.Yu. Tyulyaeva, T.N. Lomova, 2010, published in Zhurnal Fizicheskoi Khimii, 2010, Vol. 84, No. 5, pp. 847–853.

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Tyulyaeva, E.Y., Lomova, T.N. Thermodynamics and kinetics of the formation of the supramolecular complexes bisacetato(5,10,15,20-tetraphenylporphinate)zirconium(IV) with pyridine and imidazole. Russ. J. Phys. Chem. 84, 749–754 (2010). https://doi.org/10.1134/S0036024410050079

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  • DOI: https://doi.org/10.1134/S0036024410050079

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