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Acid–Base, Complexing and Spectral Properties of Thiobarbituric Acid and Its 1,3-Derivatives in Aqueous Solutions: Spectrophotometric and Quantum Chemical Approach

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Abstract

The acid–base properties of 2-thiobarbituric, 1,3-diethyl-, and 1,3-dibutyl-2-thiobarbiturc acids and the thermodynamics of their complexation with Ag(I) ions in aqueous solutions have been investigated using a spectrophotometric technique and ab initio calculations. The free acids primarily exist in keto-form and undergo enolization in neutral aqueous solutions. They undergo protonation via free oxygen atoms in acidic conditions. It has been discovered that 1,3-diethyl-2-thiobarbiturc acid behaves as a S-donor ligand under these conditions. The TD–DFT calculations of all the thiobarbiturc acids have revealed π–π* transitions from the sulfur and oxygen atoms in the ring. The complexation with Ag(I) ions lead to the transition of the z2 orbital of silver and π orbitals of sulfur into π* orbitals of a ring.

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Acknowledgments

The research has been funded and carried out in terms of state contract (No. 3049) of Ministry of Education and Science of Russian Federation. The authors would also like to thank SFU CEJU for technical support.

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Authors and Affiliations

  1. Institute of Chemistry and Chemical Technology of the Siberian Branch of the RAS, Krasnoyarsk, Russian Federation

    Maxim A. Lutoshkin & Alexandr I. Petrov

  2. Institute of Non-Ferrous Metals and Materials Science, Siberian Federal University, Krasnoyarsk, Russian Federation

    Alexandr I. Petrov & Nicolay N. Golovnev

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  1. Maxim A. Lutoshkin
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  2. Alexandr I. Petrov
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  3. Nicolay N. Golovnev
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Correspondence to Maxim A. Lutoshkin.

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Lutoshkin, M.A., Petrov, A.I. & Golovnev, N.N. Acid–Base, Complexing and Spectral Properties of Thiobarbituric Acid and Its 1,3-Derivatives in Aqueous Solutions: Spectrophotometric and Quantum Chemical Approach. J Solution Chem 45, 1453–1467 (2016). https://doi.org/10.1007/s10953-016-0525-3

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