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Formation and Evolution of H2C3O+• Radical Cations: A Computational and Matrix Isolation Studyстатья
Статья опубликована в высокорейтинговом журнале
Статья опубликована в журнале из списка Web of Science и/или Scopus- Авторы: Zasimov Pavel V., Ryazantsev Sergey V., Tyurin Daniil A., Feldman Vladimir I.
- Журнал: Journal of the American Chemical Society
- Том: 144
- Номер: 18
- Год издания: 2022
- Издательство: American Chemical Society
- Местоположение издательства: United States
- Первая страница: 8115
- Последняя страница: 8128
- DOI: 10.1021/jacs.2c00295
- Аннотация: The family of isomeric H2C3O+• radical cations is of great interest for physical organic chemistry and chemistry occurring in extraterrestrial media. In this work, we have experimentally examined a unique synthetic route to the generation of H2C3O+• from the C2H2···CO intermolecular complex and also considered the relative stability and monomolecular transformations of the H2C3O+• isomers through high-level ab initio calculations. The structures, energetics, harmonic frequencies, hyperfine coupling constants, and isomerization pathways for several of the most important H2C3O+• isomers were calculated at the UCCSD(T) level of theory. The complementary FTIR and EPR studies in argon matrices at 5 K have demonstrated that the ionized C2H2···CO complex transforms into the E-HCCHCO+• isomer, and this latter species is supposed to be the key intermediate in further chemical transformations, providing a remarkable piece of evidence for kinetic control in low-temperature chemistry. Photolysis of this species at λ = 410−465 nm results in its transformation to the thermodynamically most stable H2CCCO+• isomer. Possible implications of the results and potentiality of the proposed synthetic strategy to the preparation of highly reactive organic radical cations are discussed.
- Добавил в систему: Засимов Павел Валерьевич
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