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Study in Aqueous Solutions of Bioactive 2-Pyridineformamide-Derived Thiosemicarbazones and Their Iron(II) and Iron(III) Complexes

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Abstract

The binary systems of iron(II) and iron(III) with 2-pyridineformamide thiosemicarbazone (H2Am4DH) and its N(4)-methyl (H2Am4Me), N(4)-ethyl (H2Am4Et) and N(4)-phenyl (H2Am4Ph) derivatives were studied in aqueous solution by pH-potentiometry, ultraviolet–visible spectroscopy and EPR spectra. The formation constants of the iron(II) and iron(III) complexes were calculated from potentiometric and electronic absorption data at 25 °C and ionic strength μ = 0.1 mol·L−1 using the HYPERQUAD program. The values of the formation constant of the FeL species decrease in the order Fe:H2Am4DH > Fe:H2Am4Me ≈ Fe:H2Am4Et > Fe:H2Am4Ph in the same way as the basicity of the ligands. The species distribution diagrams show that the species FeL2 predominates at physiological pH in the Fe:H2Am4DH, Fe:H2Am4Me and Fe:H2Am4Et systems. The similar EPR spectra of these iron(III) binary systems indicate the same coordination spheres around the metallic center and the EPR g values suggests that the unpaired electron is in the dxy orbital, indicating a d 2xz d 2yz d 1xy ground state configuration for the complexes. For the Fe(III):H2Am4Ph system the EPR results indicated dimerization and antiferromagnetic interaction due to the presence of only one thiosemicarbazone ligand around the metallic center.

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Acknowledgments

This research was partially supported by grants from the Brazilian agencies FAPERJ and CNPq. We thank CBPF for the use of the EPR spectrometer.

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Authors and Affiliations

  1. Departamento de Química, Pontifícia Universidade Católica do Rio de Janeiro (PUC-Rio), Rua Marquês de São Vicente, 225, Rio de Janeiro, RJ, 22453-900, Brazil

    Felipe S. Vilhena & Judith Felcman

  2. Department of Chemistry, Universidade Federal de Minas Gerais (UFMG), Belo Horizonte, Brazil

    Letícia R. Teixeira & Heloisa Beraldo

  3. Institute of Chemistry, Universidade Federal Fluminense (UFF), Niterói, Brazil

    Odivaldo Cambraia Alves & Fabio da S. Miranda

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  1. Felipe S. Vilhena
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Correspondence to Felipe S. Vilhena.

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Vilhena, F.S., Teixeira, L.R., Alves, O.C. et al. Study in Aqueous Solutions of Bioactive 2-Pyridineformamide-Derived Thiosemicarbazones and Their Iron(II) and Iron(III) Complexes. J Solution Chem 42, 555–565 (2013). https://doi.org/10.1007/s10953-013-9977-x

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  • DOI: https://doi.org/10.1007/s10953-013-9977-x

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