Get access
Advertisement

DFT calculations of the redox potentials for the nitrosyl complexes [Fe2(μ-RS)2(NO)4] with R = alkyl

Authors

  • Nina S. Emel'yanova,

    Corresponding author
    1. Department of Substance Structure, Institute of Problems of Chemical Physics, Russian Academy of Science, Ac. Semenov Ave,1, Chernogolovka, Moscow Region 142432, Russia
    • Institute of Problems of Chemical Physics, Russian Academy of Science, Ac. Semenov Ave,1, Chernogolovka, Moscow Region 142432, Russia
    Search for more papers by this author
  • Alexander F. Shestakov,

    1. Department of Substance Structure, Institute of Problems of Chemical Physics, Russian Academy of Science, Ac. Semenov Ave,1, Chernogolovka, Moscow Region 142432, Russia
    Search for more papers by this author
  • Nataliya A. Sanina

    1. Department of Substance Structure, Institute of Problems of Chemical Physics, Russian Academy of Science, Ac. Semenov Ave,1, Chernogolovka, Moscow Region 142432, Russia
    Search for more papers by this author

Abstract

The redox potentials of alkyl substituted Roussin's red esters in tetrahydrofuran and acetonitrile were studied using the density functional theory. The geometry and electronic structures of monoanions of Roussin's red esters [Fe2(μ-RS)2(NO)4] (R = Me, Et, i-Pr, t-Bu) together with their redox potentials in solutions have been computed using GGA (BP86,PBE, BLYP), meta-GGA (TPSS), hybrid-GGA (B3LYP), and meta-hybrid GGA (BMK, B1B95) combined with 6-311++G**//6-31G* and tzvp basis set. The BP86 functional provides excellent agreement with experiment, whereas B3LYP requires some correlation, which makes it possible to estimate the redox potentials of related complexes, intermediate, or unstable. In particular, a redox potential of the complex with R = Ph, a perspective anticancer drug, has been evaluated for several solvents. © 2012 Wiley Periodicals, Inc.

Get access to the full text of this article

Ancillary