Quantum chemical modeling of ligand substitution in cationic nitrosyl iron complexes

N. S. Emel'Yanova, O. Kh Poleshchuk, N. A. Sanina, S. M. Aldoshin

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    1 Citation (Scopus)


    The substitution of the glutathione ligand for penicillamine and cysteamine ligands in the cationic nitrosyl iron complexes with the penicillamine thiyl ligand, [Fe2(SC5H11NO2)2(NO)4]SO4·2H2O, and the cysteamine thiyl ligand, [Fe2(S(CH)2NH3)2(NO)4]SO4·2H2O, was studied by quantum chemical methods. Quantum chemical calculations were performed with the full geometry optimization of the starting and final complexes by the DFT method using the local BP86 and OPBE functionals. The structures of the intermediate and final complexes were predicted. The S-C bond in the complexes with the penicillamine ligand is longer than in other complexes of this type. The calculated energy of the detachment of the ligand from the complex with penicillamine is lower than that for the complex with the cysteamine ligand. The ligand substitution in the complex with the penicillamine ligand does not require considerable energy and can easily proceed in aqueous solution, whereas this reaction in the complex with the cysteamine ligand is thermodynamically unfavorable.

    Original languageEnglish
    Pages (from-to)1088-1094
    Number of pages7
    JournalRussian Chemical Bulletin
    Issue number5
    Publication statusPublished - 1 Jan 2014


    • BP86 and OPBE functionals
    • density functional theory (DFT)
    • iron-sulfur nitrosyl complexes
    • PCM and COSMO approaches
    • solvation effects

    ASJC Scopus subject areas

    • Chemistry(all)

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