Double‐σ‐Bonded Close‐Shell Dimers and Peroxy‐Linked Open‐Shell Dimer Derived from a C3 Symmetric Trioxophenalenyl Neutral Diradical.

Autor: Murata, Tsuyoshi, Yoshida, Kenta, Suzuki, Shuichi, Ueda, Akira, Nishida, Shinsuke, Kawai, Junya, Fukui, Kozo, Sato, Kazunobu, Takui, Takeji, Nakasuji, Kazuhiro, Morita, Yasushi
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Zdroj: Chemistry - A European Journal; 9/16/2022, Vol. 28 Issue 52, p1-10, 10p
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 1H 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. [ABSTRACT FROM AUTHOR]
Databáze: Complementary Index
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