2020年3月18日
Duality of Reactivity of a Biradicaloid Compound with an o-Quinodimethane Scaffold
Journal of the American Chemical Society
- ,
- ,
- ,
- 巻
- 142
- 号
- 11
- 開始ページ
- 5408
- 終了ページ
- 5418
- 記述言語
- 掲載種別
- 研究論文(学術雑誌)
- DOI
- 10.1021/jacs.0c01003
- 出版者・発行元
- American Chemical Society ({ACS})
Sigmarene, which is a Kekulé hydrocarbon with appreciable singlet biradical character originating from an o-quinodimethane scaffold, is isolated as a doubly σ-bonded dimer. The dimer dissociates into a monomeric sigmarene upon heating or photoirradiation. The monomeric species undergoes a rapid [4 + 4] cycloaddition reaction under dark conditions even at room temperature to produce the dimer. Contrarily, the monomeric sigmarene undergoes a [4 + 2] cycloaddition reaction in the presence of dienophile as an orbital symmetry allowed process. Therefore, the sigmarene shows high reactivity for both symmetry-forbidden and allowed processes in the framework of the orbital symmetry rule. This duality of reactivity of the sigmarene is consistent with the intermediate singlet biradical character (44%) estimated by a density functional theory (DFT) calculation.
- リンク情報
- ID情報
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- DOI : 10.1021/jacs.0c01003
- ISSN : 0002-7863
- eISSN : 1520-5126
- ORCIDのPut Code : 69957937
- PubMed ID : 32096632
- SCOPUS ID : 85082097685