Double-σ-Bonded Close-Shell Dimers and Peroxy-Linked Open-Shell Dimer Derived from a C 3 Symmetric Trioxophenalenyl Neutral Diradical.

Autor: Murata T; Department of Applied Chemistry, Faculty of Engineering, Aichi Institute of Technology, Yachigusa 1247, Yakusa, Toyota, Aichi, Japan., Yoshida K; Department of Chemistry Graduate School of Science, Osaka University, Machikaneyama 1-1, Toyonaka, Osaka, Japan., Suzuki S; Department of Chemistry Graduate School of Engineering Science, Osaka University, Machikaneyama 1-3, Toyonaka, Osaka, Japan., Ueda A; Department of Chemistry Faculty of Advanced Science and Technology, Kumamoto University, 2-39-1 Kurokami, Chuo-ku, Kumamoto, Japan., Nishida S; Department of Applied Chemistry, Faculty of Engineering, Aichi Institute of Technology, Yachigusa 1247, Yakusa, Toyota, Aichi, Japan., Kawai J; Department of Chemistry Graduate School of Science, Osaka University, Machikaneyama 1-1, Toyonaka, Osaka, Japan., Fukui K; Department of Chemistry Graduate School of Science, Osaka University, Machikaneyama 1-1, Toyonaka, Osaka, Japan., Sato K; Department of Chemistry and Molecular Materials Science Graduate School of Science, Osaka City University/Osaka Metropolitan University, Sugimoto 3-3-138, Sumiyoshi-ku, Osaka, Japan., Takui T; Department of Chemistry and Molecular Materials Science Graduate School of Science, Osaka City University/Osaka Metropolitan University, Sugimoto 3-3-138, Sumiyoshi-ku, Osaka, Japan., Nakasuji K; Department of Chemistry Graduate School of Science, Osaka University, Machikaneyama 1-1, Toyonaka, Osaka, Japan., Morita Y; Department of Applied Chemistry, Faculty of Engineering, Aichi Institute of Technology, Yachigusa 1247, Yakusa, Toyota, Aichi, Japan.
Jazyk: angličtina
Zdroj: Chemistry (Weinheim an der Bergstrasse, Germany) [Chemistry] 2022 Sep 16; Vol. 28 (52), pp. e202201426. Date of Electronic Publication: 2022 Jul 26.
DOI: 10.1002/chem.202201426
Abstrakt: A novel neutral diradical of π-extended phenalenyl derivative having three oxo-groups, tri-tert-butyl-1,4,7-trioxophenalenyl, and two types of the corresponding σ-dimers were investigated. Quantum chemical calculations showed that the neutral diradical is in triplet ground state having doubly degenerate singly occupied molecular orbitals. The neutral diradical undergoes a σ-dimerization, generating two types of σ-dimers immediately after the preparation. One of the σ-dimers, which was selectively generated in the crystalline state, was a close-shell dimer linked through double-σ-bonds on the phenalenyl skeleton with a long C-C bond length of 1.66 Å. The other σ-dimer, which existed only in the solution state, was a peroxy-linked open-shell dimer in which one σ-bond was formed between two oxygen atoms. Furthermore, the temperature-dependent 1 H NMR and ESR spectra revealed that these σ-dimers are in equilibrium in the solution state by the reversible σ-bond formation/cleavage via the neutral diradical as a key intermediate.
(© 2022 Wiley-VCH GmbH.)
Databáze: MEDLINE
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