Mechanistic diversity in acetophenone transfer hydrogenation catalyzed by ruthenium iminophosphonamide complexes

Kalsin, A.M.; Peganova, T.A.; Sinopalnikova, I.S.; Fedyanin, I.V.; Natalia, B.; Eric, D.; Rinaldo, P.

Авторы: Kalsin Alexander M., Peganova Tatyana A., Sinopalnikova Iana S., Fedyanin Ivan V., Natalia Belkova, Eric Deydier, Rinaldo Poli
Журнал: Dalton Transactions
Год издания: 2020
Издательство: Royal Society of Chemistry
Местоположение издательства: United Kingdom
DOI: 10.1039/C9DT04532E
Аннотация: A series of arene ruthenium iminophosphonamide complexes, [(Arene)RuCl{R2P(NR’)2}] (1), bearing various arenes and R,R’ substituents on the NPN ligand have been investigated as precatalysts in acetophenone transfer hydrogenation in basic and base-free isopropanol. The results clearly demonstrate the presence of two distinct reaction mechanisms, which are controlled by the basicity of the N-atoms. Complexes 1 in which both R’ substituents are aryl groups are only active once the neutral hydride complex [(Arene)RuH{R2P(NR’)2}] (2) is generated in basic isopropanol, the latter being able to reduce a ketone via a stepwise hydride and proton transfer. On the other hand, complexes in which at least one R’ group is Me readily catalyze the reaction in the absence of base. In the latter case, the results of kinetic studies and DFT calculations support an outer-sphere concerted asynchronous hydrogen atoms transfer assisted by the basic N-atom of the NPN ligand, which promotes catalysis via precoordination of an alcohol molecule by hydrogen bonding.
Добавил в систему: Кальсин Александр Михайлович

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Mechanistic diversity in acetophenone transfer hydrogenation catalyzed by ruthenium iminophosphonamide complexesстатья

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