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Expanding the Role of Dimeric Species: On-Cycle Involvement, Improved Stability, and Control of Stereo-Specificity. A Case Study of Atom-Economic Catalytic Hydrothiolationстатья
Статья опубликована в высокорейтинговом журнале
Информация о цитировании статьи получена из
Scopus
Статья опубликована в журнале из списка Web of Science и/или Scopus
Дата последнего поиска статьи во внешних источниках: 26 июня 2024 г.
- Авторы: Sahharova Liliya T., Burykina Julia V., Kostyukovich Alexander Yu, Eremin Dmitry B., Boiko Daniil A., Fakhrutdinov Artem N., Ananikov Valentine P.
- Журнал: ACS catalysis
- Том: 13
- Год издания: 2023
- Издательство: American Chemical Society
- Местоположение издательства: United States
- Первая страница: 3591
- Последняя страница: 3604
- DOI: 10.1021/acscatal.2c06406
- Аннотация: A common assumption that dimeric metal complexes in many catalytic systems represent a resting state and are not directly involved in catalytic processes was revised in a combined experimental and theoretical study. On-cycle participation of dimeric metal complexes, rather than typically assumed off-cycle involvement, was revealed, and advantageous performance in terms of improved selectivity was observed. The conceptual rationalization for the participation of dimeric species in the catalytic cycle was developed. The Pd-catalyzed hydrothiolation process (where strong Pd–S binding is well established and a persistent opinion for the inactive/poisoning role of dimeric species is presumed) was evaluated as a challenging system to test the concept. Activation of an (NHC)Pd(Cl)(acac) precatalyst (NHC─N-heterocyclic carbene and acac─acetylacetonate) under the reaction conditions produced monomeric (NHC)Pd(SPh)2 or dimeric (NHC)2Pd2(SPh)4 species depending on the steric bulkiness of the NHC ligand. Dimeric complexes possessed higher selectivity and tolerated disulfide impurities in contrast to monomeric complexes. Quantum chemical modeling suggested that dimeric catalysis proceeds through the opening of only one (μ-SPh)–Pd bridging bond with retention of the dimeric structure. The second bridging bond is maintained, which prevents the monomerization of the complex. Catalytically active species were detected in a hydrothiolation reaction by high-resolution mass spectrometry and NMR spectroscopy. Proving the opportunity for productive homogeneous catalysis via strongly coordinated dimeric metal species opens new opportunities for catalyst design in the increased nuclearity dimension.
- Добавил в систему: Анаников Валентин Павлович