Russian Chemical Bulletin

, Volume 61, Issue 10, pp 1860–1866 | Cite as

Redox properties of [Fe2(SC6H5)2(NO)4]: an experimental study and quantum chemical modeling

  • N. A. Sanina
  • A. G. Krivenko
  • R. A. Manzhos
  • N. S. Emel’yanova
  • K. V. Bozhenko
  • S. M. Aldoshin
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Abstract

Reduction of the complex [Fe2(SC6H5)2(NO)4] in an aprotic solvent was studied by cyclic voltammetry in a wide range of potential scan rates. It was established that transfer of the first electron is reversible and the redox potential of this reaction was determined. Further reduction of the complex is irreversible because the product of attachment of the second electron is unstable and partially decomposes during the characteristic time of potential scan. The molecular and electronic structures of mono- and dianion of the complex as well as its theoretical redox potential value were calculated using the density functional theory methods with the local (BP86) and hybrid (B3LYP) functionals. The former functional better describes the geometry of the complex while the latter gives a better insight into its electronic structure. The extra negative charge is delocalized over NO groups, phenyl ligands, and iron atoms. The calculated redox potentials of one-electron reduction of the complexes are close to the experimental values obtained by analyzing cyclic voltammograms. Attachment of the second electron opens the decomposition channel of the complex, which is also consistent with experimental data.

Key words

nitrosyl complexes electron transfer cyclic voltammetry redox potential density functional theory molecular and electronic structure 
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Copyright information

© Springer Science+Business Media New York 2012

Authors and Affiliations

  • N. A. Sanina
    • 1
  • A. G. Krivenko
    • 1
  • R. A. Manzhos
    • 1
  • N. S. Emel’yanova
    • 1
  • K. V. Bozhenko
    • 1
  • S. M. Aldoshin
    • 1
  1. 1.Institute of Problems of Chemical PhysicsRussian Academy of SciencesChernogolovka, Moscow RegionRussian Federation

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