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Detection and Structural Investigation of Elusive Palladium Hydride Intermediates Formed from Simple Metal Saltsстатья Исследовательская статья
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: 30 июня 2021 г.
- Авторы: Kostyukovich Alexander Yu, Burykina Julia V., Eremin Dmitry B., Ananikov Valentine P.
- Журнал: Inorganic Chemistry
- Том: 60
- Номер: 10
- Год издания: 2021
- Издательство: American Chemical Society
- Местоположение издательства: United States
- Первая страница: 7128
- Последняя страница: 7142
- DOI: 10.1021/acs.inorgchem.1c00173
- Аннотация: The Mizoroki–Heck reaction is one of the most known and best studied catalytic transformations and has provided an outstanding driving force for the development of catalysis and synthetic applications. Three out of four classical Mizoroki–Heck catalytic cycle intermediates contain Pd–C bonds and are well known and studied in detail. However, a simple palladium hydride (which is formed after the product-releasing β-H-elimination step) is a kind of elusive intermediate in the Mizoroki–Heck reaction. In the present study, we performed a combined theoretical and mass spectrometry (MS) study of palladium hydride complexes [PdX2H]− (X = Cl, Br, and I), which are reactive intermediates in the Mizoroki–Heck reaction. Static and molecular dynamic calculations revealed that these species have a T-shaped structure with a trans-arrangement of halogen atoms. Other isomers of [PdX2H]− are unstable and easily rearrange into the T-shaped form or decompose. These palladium hydride intermediates were detected by MS in precatalyst activation using NaBH4, Et3N, and a solvent molecule as reducing agents. Online MS monitoring allowed the detection of [PdX2H]− species in the course of the Mizoroki–Heck reaction.
- Добавил в систему: Анаников Валентин Павлович