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Mechanistic Study in Azide-Alkyne Cycloaddition (CuAAC) Catalyzed by Bifunctional Trinuclear Copper(I) Pyrazolate Complex: Shift in Rate-Determining Stepстатья
Статья опубликована в высокорейтинговом журнале
Информация о цитировании статьи получена из
Web of Science,
Scopus
Статья опубликована в журнале из списка Web of Science и/или Scopus
Дата последнего поиска статьи во внешних источниках: 7 октября 2020 г.
- Авторы: Larionov Vladimir A., Stashneva Anna R., Titov Aleksei A., Lisov Alexey A., Medvedev Michael G., Smol’yakov Alexander F., Tsedilin Andrey M., Shubina Elena S., Maleev Victor I.
- Журнал: Journal of Catalysis
- Том: 390
- Год издания: 2020
- Издательство: Academic Press
- Местоположение издательства: United States
- Первая страница: 37
- Последняя страница: 45
- DOI: 10.1016/j.jcat.2020.07.010
- Аннотация: Trinuclear copper(I) pyrazolate [Cu(3,5-CF3)2Pz)]3 was employed in a mechanistic study of azide-alkyne cycloaddition (CuAAC). It was shown that the copper complex operates as a bifunctional catalytic system (copper source and Brønsted base) under mild conditions (RT and air atmosphere) at low catalyst loading (1 mol%). The rate-determining step of the reaction is the first C-N bond formation between azide and acetylene (azide migratory insertion) but not the copper(I) acetylide formation as commonly assumed. It was supported by the observed kinetic isotope effect equaling 1.1 and by DFT calculations. The reactionhas a second-order dependence on the catalyst concentration implicating the two copper(I) centers participate in the metallacycle formation step from ‘‘bis-butterfly” tetranuclear complex Cu4L4(RCCH)2 in the rate-determining step. DFT calculations proved that the pyrazolate ligand acts as a Brønsted base and deprotonates the acetylene molecule providing successful catalysis. A plausible catalytic cycle of the reaction has constructed based on DFT calculations.
- Добавил в систему: Ларионов Владимир Анатольевич
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