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Pd and Pt Catalyst Poisoning in the Study of Reaction Mechanisms: What Does the Mercury Test Mean for Catalysis?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: 3 марта 2021 г.
- Авторы: Chernyshev Victor M., Astakhov Alexander V., Chikunov Ilya E., Tyurin Roman V., Eremin Dmitry B., Ranny Gleb S., Khrustalev Victor N., Ananikov Valentine P.
- Журнал: ACS catalysis
- Том: 9
- Номер: 4
- Год издания: 2019
- Издательство: American Chemical Society
- Местоположение издательства: United States
- Первая страница: 2984
- Последняя страница: 2995
- DOI: 10.1021/acscatal.8b03683
- Аннотация: The mercury test is a rapid and widely used method for distinguishing truly homogeneous molecular catalysis from nanoparticle metal catalysis. In the current work, using various M0 and MII complexes of palladium and platinum that are often used in homogeneous catalysis as examples, we demonstrated that the mercury test is generally inadequate as a method for distinguishing between homogeneous and cluster/nanoparticle catalysis mechanisms for the following reasons: (i) the general and facile reactivity of both molecular M0 and MII complexes toward metallic mercury and (ii) the very high and often unpredictable dependence of the test results on the operational conditions and the inability to develop universal quantitatively defined operational parameters. Two main types or mercury-induced transformations, the cleavage of M0 complexes and the oxidative–reductive transmetalation of MII complexes, including a reaction of highly popular MII/NHC complexes, were elucidated using NMR, ESI-MS, and EDXRF techniques. A mechanistic picture of the reactions involving metal complexes was revealed with mercury, and representative metal species were isolated and characterized. Even in an attempt to not overstate the results, one must note that the use of the mercury tests often leads to inaccurate conclusions and complicates the mechanistic studies of these catalytic systems. As a general concept, distinguishing reaction mechanisms (homogeneous vs cluster/nanoparticle) by using catalyst poisoning requires careful rethinking in the case of dynamic catalytic systems.
- Добавил в систему: Анаников Валентин Павлович