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Complexation of Zn(II) and Cu(II) by Perfluorinated β-Diketones: Theoretical and Experimental Approaches and Potential Use as Copper-Eliminating Agents

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Abstract

Aqueous chelation of six perfluorinated β-diketones with copper(II) and zinc(II) was studied under various conditions. Complexation with thenoyl-trifluoroacetone, furoyl-trifluoroacetone, selenoyl-trifluroacetone, phenyl-trifluoroacetone, para-chloro-phenyl-trifluoroacetone, and para-fluoro-phenyl-trifluoroacetone have been investigated spectrophotometrically and theoretically to understand the mechanism of complexation with bivalent copper and zinc ions. The spectral dataset has been processed using non-linear regression analysis and methods of linear algebra and the structures of the formed complexes have been established. By variation of pH, concentration of side ions and ionic strength, the mechanism of the chelation was investigated and detailed. Interaction with Zn(II) and Cu(II) leads to the formation of monocomplex species with various compositions. Conditional and some “true” stability constants were determined at various conditions. Studied ligands show an unusual chelation behavior: in the pH region 1–5 interaction with rare earth metals, Zn2+ and Cu2+ were detected, but complexation with Pb2+ and Cd2+ has not been observed. Thus, “anti-selectivity” toward some transition metals was shown under specific conditions. Also, all ligands demonstrate significant selectivity to Cu(II). Spectral and thermodynamic characteristics have been estimated using ab initio computations.

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Acknowledgements

This work was conducted within the framework of the budget project 0287-2021-0012 for Institute of Chemistry and Chemical Technology SB RAS using the equipment of Krasnoyarsk Regional Research Equipment Centre of SB RAS. Synthetic part of this work was financially supported by the Russian Science Foundation (Project №19-13-00272). Numerical computations were performed on the MVS-1000M cluster of the Institute of computational modeling SB RAS.

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Authors and Affiliations

  1. Institute of Chemistry and Chemical Technology SB RAS, Federal Research Center “Krasnoyarsk Science Center SB RAS”, Krasnoyarsk, Russian Federation

    Maxim A. Lutoshkin

  2. Krasnoyarsk State Medical University Named After V.F. Voino-Yasenetsky, Krasnoyarsk, Russian Federation

    Maxim A. Lutoshkin

  3. P. N. Lebedev Institute of Physics of the , Russian Academy of Sciences, Moscow, Russian Federation

    Ilya V. Taydakov

  4. G.V. Plekhanov, Russian University of Economics, Moscow, Russian Federation

    Ilya V. Taydakov

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Lutoshkin, M.A., Taydakov, I.V. Complexation of Zn(II) and Cu(II) by Perfluorinated β-Diketones: Theoretical and Experimental Approaches and Potential Use as Copper-Eliminating Agents. J Solution Chem 52, 304–325 (2023). https://doi.org/10.1007/s10953-022-01233-4

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