Theoretical Study of Bond-Switching in 1,6-Dihydro-6athia-1,6- diazapentalene (10-S-3) Systems Compared with Corresponding Oxygen Analogues

Teruo Atsumi, Tomohiro Abe, Kin Ya Akiba, Hiromi Nakai

    Research output: Contribution to journalArticle

    6 Citations (Scopus)

    Abstract

    Theoretical study of the mechanism of bond-switching of 5-(1-aminoethylimino)-3-methyl-1,2,4-thiadiazole and 5-(2-aminovinyl)isothiazole was carried out by using simplified models of 1,6-dihydro-6a-thia-1,6- diazapentalene (10-S-3) systems and corresponding oxygen analogs. Geometries and energetics were examined along unimolecular and bimolecular reaction paths by hybrid density functional theory (DFT) calculations with triple-zeta class basis sets by taking into account solvent effects which is estimated by the polarizable continuum model. It was clarified that the unimolecular reactions cannot proceed due to the high energy barriers around 70 kcalmol-1. On the other hand, the bimolecular processes in neutral and acidic conditions can be accomplished for the sulfur compounds, not for the oxygen ones. The differences of the reactivities between the sulfur and oxygen compounds were found to be due to the difference of the stability of the symmetric intermediates with the hypervalent three-center four-electron bonds.

    Original languageEnglish
    Pages (from-to)520-529
    Number of pages10
    JournalBulletin of the Chemical Society of Japan
    Volume83
    Issue number5
    DOIs
    Publication statusPublished - 2010

    Fingerprint

    Sulfur Compounds
    Oxygen Compounds
    Thiadiazoles
    Oxygen
    Energy barriers
    Density functional theory
    Geometry
    Electrons

    ASJC Scopus subject areas

    • Chemistry(all)

    Cite this

    Theoretical Study of Bond-Switching in 1,6-Dihydro-6athia-1,6- diazapentalene (10-S-3) Systems Compared with Corresponding Oxygen Analogues. / Atsumi, Teruo; Abe, Tomohiro; Akiba, Kin Ya; Nakai, Hiromi.

    In: Bulletin of the Chemical Society of Japan, Vol. 83, No. 5, 2010, p. 520-529.

    Research output: Contribution to journalArticle

    @article{227b764fff7c49bd9b101c1b04d8f663,
    title = "Theoretical Study of Bond-Switching in 1,6-Dihydro-6athia-1,6- diazapentalene (10-S-3) Systems Compared with Corresponding Oxygen Analogues",
    abstract = "Theoretical study of the mechanism of bond-switching of 5-(1-aminoethylimino)-3-methyl-1,2,4-thiadiazole and 5-(2-aminovinyl)isothiazole was carried out by using simplified models of 1,6-dihydro-6a-thia-1,6- diazapentalene (10-S-3) systems and corresponding oxygen analogs. Geometries and energetics were examined along unimolecular and bimolecular reaction paths by hybrid density functional theory (DFT) calculations with triple-zeta class basis sets by taking into account solvent effects which is estimated by the polarizable continuum model. It was clarified that the unimolecular reactions cannot proceed due to the high energy barriers around 70 kcalmol-1. On the other hand, the bimolecular processes in neutral and acidic conditions can be accomplished for the sulfur compounds, not for the oxygen ones. The differences of the reactivities between the sulfur and oxygen compounds were found to be due to the difference of the stability of the symmetric intermediates with the hypervalent three-center four-electron bonds.",
    author = "Teruo Atsumi and Tomohiro Abe and Akiba, {Kin Ya} and Hiromi Nakai",
    year = "2010",
    doi = "10.1246/bcsj.20100006",
    language = "English",
    volume = "83",
    pages = "520--529",
    journal = "Bulletin of the Chemical Society of Japan",
    issn = "0009-2673",
    publisher = "Chemical Society of Japan",
    number = "5",

    }

    TY - JOUR

    T1 - Theoretical Study of Bond-Switching in 1,6-Dihydro-6athia-1,6- diazapentalene (10-S-3) Systems Compared with Corresponding Oxygen Analogues

    AU - Atsumi, Teruo

    AU - Abe, Tomohiro

    AU - Akiba, Kin Ya

    AU - Nakai, Hiromi

    PY - 2010

    Y1 - 2010

    N2 - Theoretical study of the mechanism of bond-switching of 5-(1-aminoethylimino)-3-methyl-1,2,4-thiadiazole and 5-(2-aminovinyl)isothiazole was carried out by using simplified models of 1,6-dihydro-6a-thia-1,6- diazapentalene (10-S-3) systems and corresponding oxygen analogs. Geometries and energetics were examined along unimolecular and bimolecular reaction paths by hybrid density functional theory (DFT) calculations with triple-zeta class basis sets by taking into account solvent effects which is estimated by the polarizable continuum model. It was clarified that the unimolecular reactions cannot proceed due to the high energy barriers around 70 kcalmol-1. On the other hand, the bimolecular processes in neutral and acidic conditions can be accomplished for the sulfur compounds, not for the oxygen ones. The differences of the reactivities between the sulfur and oxygen compounds were found to be due to the difference of the stability of the symmetric intermediates with the hypervalent three-center four-electron bonds.

    AB - Theoretical study of the mechanism of bond-switching of 5-(1-aminoethylimino)-3-methyl-1,2,4-thiadiazole and 5-(2-aminovinyl)isothiazole was carried out by using simplified models of 1,6-dihydro-6a-thia-1,6- diazapentalene (10-S-3) systems and corresponding oxygen analogs. Geometries and energetics were examined along unimolecular and bimolecular reaction paths by hybrid density functional theory (DFT) calculations with triple-zeta class basis sets by taking into account solvent effects which is estimated by the polarizable continuum model. It was clarified that the unimolecular reactions cannot proceed due to the high energy barriers around 70 kcalmol-1. On the other hand, the bimolecular processes in neutral and acidic conditions can be accomplished for the sulfur compounds, not for the oxygen ones. The differences of the reactivities between the sulfur and oxygen compounds were found to be due to the difference of the stability of the symmetric intermediates with the hypervalent three-center four-electron bonds.

    UR - http://www.scopus.com/inward/record.url?scp=77952401476&partnerID=8YFLogxK

    UR - http://www.scopus.com/inward/citedby.url?scp=77952401476&partnerID=8YFLogxK

    U2 - 10.1246/bcsj.20100006

    DO - 10.1246/bcsj.20100006

    M3 - Article

    AN - SCOPUS:77952401476

    VL - 83

    SP - 520

    EP - 529

    JO - Bulletin of the Chemical Society of Japan

    JF - Bulletin of the Chemical Society of Japan

    SN - 0009-2673

    IS - 5

    ER -