Journal of Solution Chemistry

, Volume 42, Issue 3, pp 555–565 | Cite as

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

  • Felipe S. Vilhena
  • Letícia R. Teixeira
  • Odivaldo Cambraia Alves
  • Heloisa Beraldo
  • Fabio da S. Miranda
  • Judith Felcman
Article
First Online:
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Accepted:

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 xz 2 d yz 2 d xy 1 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.

Keywords

2-Pyridineformamide thiosemicarbazones Iron complexes Stability constants EPR spectroscopy 
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Notes

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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Copyright information

© Springer Science+Business Media New York 2013

Authors and Affiliations

  • Felipe S. Vilhena
    • 1
  • Letícia R. Teixeira
    • 2
  • Odivaldo Cambraia Alves
    • 3
  • Heloisa Beraldo
    • 2
  • Fabio da S. Miranda
    • 3
  • Judith Felcman
    • 1
  1. 1.Departamento de QuímicaPontifícia Universidade Católica do Rio de Janeiro (PUC-Rio)Rio de JaneiroBrazil
  2. 2.Department of ChemistryUniversidade Federal de Minas Gerais (UFMG)Belo HorizonteBrazil
  3. 3.Institute of ChemistryUniversidade Federal Fluminense (UFF)NiteróiBrazil

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