Quantum chemical approaches to the explanation of differences in NO-donor activity of iron-sulfur nitrosyl complexes

N. S. Emel'yanova, O. Kh Poleshchuk, N. A. Sanina, K. V. Bozhenko, S. M. Aldoshin

    Research output: Contribution to journalArticle

    Abstract

    The geometries and electronic structures of ironsulfur nitrosyl complexes with aza heterocyclic thiols with μ-SCN bridging ligands, [Fe 2(SCN4Ph)2(NO)4] (1) and [Fe 2(SCN4Me)2(NO)4] (2), were calculated within the framework of the density functional theory (DFT) with the BP86, TPSS, B3LYP, and OPBE functionals in order to explain differ ences in their NOdonor activities. Chemical bonding in the complexes was analyzed using the NBO approach, according to Mulliken, and using the Voronoi scheme. NBO analysis of com plex 1 revealed a strong interaction between orbitals of the lone electron pairs of the Fe atom and the antibonding orbitals of the Fe-N bond which leads to strengthening of the Fe-NO bond. In complex 2, the Fe-NO bond is more polar than in complex 1.

    Original languageEnglish
    Pages (from-to)37-42
    Number of pages6
    JournalRussian Chemical Bulletin
    Volume63
    Issue number1
    DOIs
    Publication statusPublished - 2014

    Fingerprint

    Sulfur
    Sulfhydryl Compounds
    Electronic structure
    Density functional theory
    Iron
    Ligands
    Atoms
    Geometry
    Electrons

    Keywords

    • And B3LYP functionals
    • BP86
    • Density functional theory
    • Iron-sulfur nitrosyl complexes
    • NBO method
    • NO-donor activity
    • OPBE
    • TPSS
    • Voronoi scheme
    • Wiberg index

    ASJC Scopus subject areas

    • Chemistry(all)

    Cite this

    Quantum chemical approaches to the explanation of differences in NO-donor activity of iron-sulfur nitrosyl complexes. / Emel'yanova, N. S.; Poleshchuk, O. Kh; Sanina, N. A.; Bozhenko, K. V.; Aldoshin, S. M.

    In: Russian Chemical Bulletin, Vol. 63, No. 1, 2014, p. 37-42.

    Research output: Contribution to journalArticle

    Emel'yanova, N. S. ; Poleshchuk, O. Kh ; Sanina, N. A. ; Bozhenko, K. V. ; Aldoshin, S. M. / Quantum chemical approaches to the explanation of differences in NO-donor activity of iron-sulfur nitrosyl complexes. In: Russian Chemical Bulletin. 2014 ; Vol. 63, No. 1. pp. 37-42.
    @article{020d364971cb4715a8f31c42635d71bd,
    title = "Quantum chemical approaches to the explanation of differences in NO-donor activity of iron-sulfur nitrosyl complexes",
    abstract = "The geometries and electronic structures of ironsulfur nitrosyl complexes with aza heterocyclic thiols with μ-SCN bridging ligands, [Fe 2(SCN4Ph)2(NO)4] (1) and [Fe 2(SCN4Me)2(NO)4] (2), were calculated within the framework of the density functional theory (DFT) with the BP86, TPSS, B3LYP, and OPBE functionals in order to explain differ ences in their NOdonor activities. Chemical bonding in the complexes was analyzed using the NBO approach, according to Mulliken, and using the Voronoi scheme. NBO analysis of com plex 1 revealed a strong interaction between orbitals of the lone electron pairs of the Fe atom and the antibonding orbitals of the Fe-N bond which leads to strengthening of the Fe-NO bond. In complex 2, the Fe-NO bond is more polar than in complex 1.",
    keywords = "And B3LYP functionals, BP86, Density functional theory, Iron-sulfur nitrosyl complexes, NBO method, NO-donor activity, OPBE, TPSS, Voronoi scheme, Wiberg index",
    author = "Emel'yanova, {N. S.} and Poleshchuk, {O. Kh} and Sanina, {N. A.} and Bozhenko, {K. V.} and Aldoshin, {S. M.}",
    year = "2014",
    doi = "10.1007/s11172-014-0391-3",
    language = "English",
    volume = "63",
    pages = "37--42",
    journal = "Russian Chemical Bulletin",
    issn = "1066-5285",
    publisher = "Springer New York",
    number = "1",

    }

    TY - JOUR

    T1 - Quantum chemical approaches to the explanation of differences in NO-donor activity of iron-sulfur nitrosyl complexes

    AU - Emel'yanova, N. S.

    AU - Poleshchuk, O. Kh

    AU - Sanina, N. A.

    AU - Bozhenko, K. V.

    AU - Aldoshin, S. M.

    PY - 2014

    Y1 - 2014

    N2 - The geometries and electronic structures of ironsulfur nitrosyl complexes with aza heterocyclic thiols with μ-SCN bridging ligands, [Fe 2(SCN4Ph)2(NO)4] (1) and [Fe 2(SCN4Me)2(NO)4] (2), were calculated within the framework of the density functional theory (DFT) with the BP86, TPSS, B3LYP, and OPBE functionals in order to explain differ ences in their NOdonor activities. Chemical bonding in the complexes was analyzed using the NBO approach, according to Mulliken, and using the Voronoi scheme. NBO analysis of com plex 1 revealed a strong interaction between orbitals of the lone electron pairs of the Fe atom and the antibonding orbitals of the Fe-N bond which leads to strengthening of the Fe-NO bond. In complex 2, the Fe-NO bond is more polar than in complex 1.

    AB - The geometries and electronic structures of ironsulfur nitrosyl complexes with aza heterocyclic thiols with μ-SCN bridging ligands, [Fe 2(SCN4Ph)2(NO)4] (1) and [Fe 2(SCN4Me)2(NO)4] (2), were calculated within the framework of the density functional theory (DFT) with the BP86, TPSS, B3LYP, and OPBE functionals in order to explain differ ences in their NOdonor activities. Chemical bonding in the complexes was analyzed using the NBO approach, according to Mulliken, and using the Voronoi scheme. NBO analysis of com plex 1 revealed a strong interaction between orbitals of the lone electron pairs of the Fe atom and the antibonding orbitals of the Fe-N bond which leads to strengthening of the Fe-NO bond. In complex 2, the Fe-NO bond is more polar than in complex 1.

    KW - And B3LYP functionals

    KW - BP86

    KW - Density functional theory

    KW - Iron-sulfur nitrosyl complexes

    KW - NBO method

    KW - NO-donor activity

    KW - OPBE

    KW - TPSS

    KW - Voronoi scheme

    KW - Wiberg index

    UR - http://www.scopus.com/inward/record.url?scp=84906848382&partnerID=8YFLogxK

    UR - http://www.scopus.com/inward/citedby.url?scp=84906848382&partnerID=8YFLogxK

    U2 - 10.1007/s11172-014-0391-3

    DO - 10.1007/s11172-014-0391-3

    M3 - Article

    AN - SCOPUS:84906848382

    VL - 63

    SP - 37

    EP - 42

    JO - Russian Chemical Bulletin

    JF - Russian Chemical Bulletin

    SN - 1066-5285

    IS - 1

    ER -