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Reversible σ-Bond Formation in Bowl-Shaped π-Radical Cations: The Effects of Curved and Planar Structures
http://hdl.handle.net/2237/00028421
http://hdl.handle.net/2237/000284210947ac15-ce8a-4979-8986-78e1f684918a
名前 / ファイル | ライセンス | アクション |
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Item type | 学術雑誌論文 / Journal Article(1) | |||||
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公開日 | 2018-08-06 | |||||
タイトル | ||||||
タイトル | Reversible σ-Bond Formation in Bowl-Shaped π-Radical Cations: The Effects of Curved and Planar Structures | |||||
言語 | en | |||||
著者 |
Yokoi, Hiroki
× Yokoi, Hiroki× Hiroto, Satoru× Shinokubo, Hiroshi |
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アクセス権 | ||||||
アクセス権 | open access | |||||
アクセス権URI | http://purl.org/coar/access_right/c_abf2 | |||||
権利 | ||||||
言語 | en | |||||
権利情報 | “This document is the Accepted Manuscript version of a Published Work that appeared in final form in [Journal of the American Chemical Society], copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see [http://pubs.acs.org/articlesonrequest/AOR-NfW9REWxjIetX62GFwqd].” | |||||
抄録 | ||||||
内容記述 | The reversible formation of σ-bonds between organic radicals has been widely investigated. However, reports on the formation of σ-dimers from delocalized π-radical cations are scarce. Herein, we report the reversible σ-dimerization behavior of a bowl-shaped π-radical cation generated from a nitrogen-embedded buckybowl, both in the crystalline state and in solution. The detailed structure of the σ-dimer in the crystalline state was determined by a single-crystal X-ray diffraction analysis. The monomeric radical cation exists predominantly in solution at room temperature, while dimerization of the radical cations occurs through carbon–carbon σ-bond formation upon reducing the temperature. 1H NMR and optical spectroscopy measurements confirmed the formation of a σ-dimer at low temperature. Comparative studies with a similar yet planar π-conjugated system suggested that the curved structure of the bowl-shaped π-radical cation facilitates the σ-dimerization at one of the internal sp^2-hybridized carbon atoms. This trend was also observed for the nucleophilic addition reaction of methanol to the π-radical cations. The methoxylation reaction proceeded only for the curved π-radical cation. Theoretical calculations revealed that the large relief of structural strain at the α-carbon atom during the dimerization or nucleophilic addition reactions accelerated the bond formation at the internal carbon atom of the curved radical cation. | |||||
言語 | en | |||||
内容記述タイプ | Abstract | |||||
内容記述 | ||||||
内容記述 | ファイル公開:2019/04/04 | |||||
言語 | ja | |||||
内容記述タイプ | Other | |||||
出版者 | ||||||
言語 | en | |||||
出版者 | ACS Publications | |||||
言語 | ||||||
言語 | eng | |||||
資源タイプ | ||||||
資源タイプresource | http://purl.org/coar/resource_type/c_6501 | |||||
タイプ | journal article | |||||
出版タイプ | ||||||
出版タイプ | AM | |||||
出版タイプResource | http://purl.org/coar/version/c_ab4af688f83e57aa | |||||
DOI | ||||||
関連タイプ | isVersionOf | |||||
識別子タイプ | DOI | |||||
関連識別子 | https://doi.org/10.1021/jacs.8b00798 | |||||
ISSN | ||||||
収録物識別子タイプ | PISSN | |||||
収録物識別子 | 0002-7863 | |||||
書誌情報 |
en : Journal of the American Chemical Society 巻 140, 号 13, p. 4649-4655, 発行日 2018-04-04 |
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著者版フラグ | ||||||
値 | author |