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Thermodynamics of Dissociation of ortho-Hydroxyphenylhydrazo-β-diketones and of Their Complexation with Copper(II) in Aqueous–Ethanol Solutions

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Abstract

The thermodynamics of dissociation of 3-(2-hydroxyphenylhydrazo)pentane-2,4-dione (H 2 L 1), 5,5-dimethyl-2-(2-hydroxyphenylhydrazo)cyclohexane-1,3-dione (H 2 L 2), 5,5-dimethyl-2-(2-hydroxy-4-nitrophenylhydrazo)cyclohexane-1,3-dione (H 2 L 3), 1-ethoxy-2-(2-hydroxyphenylhydrazo)butane-1,3-dione (H 2 L 4) and 1-ethoxy-2-(2-hydroxy-4-nitrophenylhydrazo)butane-1,3-dione (H 2 L 5) and of their complexation with copper(II) was studied in aqueous–ethanol solutions by potentiometry and UV–vis spectrophotometry. It was found that the thermodynamic parameters of the proton dissociation in H2L1–5 and of their complexation with copper(II) depend on the substituents in the aromatic and β-diketone fragments of the molecules. Thus, the acidic properties of H2L increase from H2L1 to H2L5, reflecting the electron-acceptor character of the substituents, whereas all of the thermodynamic functions tend to decrease with increasing electron-withdrawing capacity of the substituents. The complexation of Cu(II) with H2L1–5 is exothermic, which is connected with the formation of two stable chelating cycles.

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Acknowledgements

This work has been partially supported by the Foundation for Science and Technology (FCT), Portugal, and its PPCDT (FEDER funded). K.T.M. expresses gratitude to the FCT for the post-doc fellowship. M.N.K. is grateful to the FCT and IST for a research contract within the Ciência 2008 scientific program.

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Authors and Affiliations

  1. Centro de Química Estrutural, Complexo I, Instituto Superior Técnico, TU Lisbon, Av. Rovisco Pais, 1049-001, Lisbon, Portugal

    Kamran T. Mahmudov, Maximilian N. Kopylovich, Maxim L. Kuznetsov & Armando J. L. Pombeiro

  2. Baku State University, Av. Z. Xalilov 23, 1148, Baku, Azerbaijan

    Abel M. Maharramov, Rafiga A. Aliyeva, Ismayil A. Aliyev & Abdulseyid A. Azizov

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  1. Kamran T. Mahmudov
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  2. Maximilian N. Kopylovich
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  3. Maxim L. Kuznetsov
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  4. Abel M. Maharramov
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  5. Rafiga A. Aliyeva
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  7. Abdulseyid A. Azizov
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  8. Armando J. L. Pombeiro
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Correspondence to Armando J. L. Pombeiro.

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Mahmudov, K.T., Kopylovich, M.N., Kuznetsov, M.L. et al. Thermodynamics of Dissociation of ortho-Hydroxyphenylhydrazo-β-diketones and of Their Complexation with Copper(II) in Aqueous–Ethanol Solutions. J Solution Chem 41, 491–502 (2012). https://doi.org/10.1007/s10953-012-9816-5

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