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Influence of R–NHC Coupling on the Outcome of R–X Oxidative Addition to Pd/NHC Complexes (R = Me, Ph, Vinyl, Ethynyl)статья Исследовательская статья
Статья опубликована в высокорейтинговом журнале
Информация о цитировании статьи получена из
Web of Science
Статья опубликована в журнале из списка Web of Science и/или Scopus
Дата последнего поиска статьи во внешних источниках: 30 апреля 2021 г.
- Авторы: Gordeev Evgeniy G., Eremin Dmitry B., Chernyshev Victor M., Ananikov Valentine P.
- Журнал: Organometallics
- Том: 37
- Номер: 5
- Год издания: 2017
- Издательство: American Chemical Society
- Местоположение издательства: United States
- Первая страница: 787
- Последняя страница: 796
- DOI: 10.1021/acs.organomet.7b00669
- Аннотация: Oxidative addition of organic halides (R–X) to (NHC)Pd0L complexes is involved in numerous metal-catalyzed reactions, and this step is expected to afford (NHC)PdII(R)(X)L intermediate complexes. However, these complexes may undergo further transformation via R–NHC coupling, which removes the NHC ligands from the metal and results in the generation of “bare” NHC-free metal species. The comparative theoretical study carried out in the present work revealed that the kinetic and thermodynamic stability of the (NHC)PdII(R)(X)L oxidative addition intermediates depends strongly on the nature of the organic group R. The predicted reactivity in the R–NHC coupling process decreases in the following order: R = Vinyl > Ethynyl > Ph > Me. Accordingly, for R = Me, a classical (NHC)PdII(R)(X)L intermediate can be expected as a product of the oxidative addition step, whereas for R = Ph, the outcome of the oxidative addition may already contain the NHC-free palladium complex. For R = Ethynyl, comparable amounts of both complexes should be formed, while for R = Vinyl, the NHC-free palladium complex can be the major product of the oxidative addition process. Unusual thermodynamic and kinetic instability of the (NHC)Pd(vinyl)(X)L complex and the tendency to vinyl–NHC coupling predicted by the computational modeling has been confirmed by experimental measurements with online mass spectrometric reaction monitoring. Thus, the outcome of the oxidative addition strongly depends on the type of organic group R and the R–NHC coupling process greatly influences the activity and stability of metal catalysts.
- Добавил в систему: Анаников Валентин Павлович