Chloride-Assisted Transfer Hydrogenation of Ketones by Half-Sandwich Rhodium Iminophosphonamide Complexes

Nekrasov, R.I.; Peganova, T.A.; Strelkova, T.V.; Gutsul, E.I.; Filippov, O.A.; Belkova, N.V.; Kalsin, A.M.

Авторы: Nekrasov R.I., Peganova T.A., Strelkova T.V., Gutsul E.I., Filippov O.A., Belkova N.V., Kalsin A.M.
Журнал: ChemCatChem
Год издания: 2025
Издательство: WILEY-VCH
Местоположение издательства: INC, 605 THIRD AVE, NEW YORK, USA, NY, 10158-0012
DOI: 10.1002/cctc.202401692
Аннотация: Half-sandwich 18e rhodium iminophosphonamide complexes [Сp*RhCl(NPN)] with NPN = Ph2P(N-p-Tol)2 (1a), Ph2P(N-p-Tol)(NMe) (1b) and 16e cationic [Сp*Rh(NPN)](PF6) (2a+PF6-) were found to catalyze transfer hydrogenation of carbonylic substrates (acyclic and cyclic alkyl ketones, aromatic ketones and aldehydes) with the activity strongly enhanced by the presence of chloride ligand. Kinetic studies including KIE and activation parameters measurements carried out for two model ketones (acetophenone and cyclohexanone) as well as model spectroscopic investigation accompanied with the DFT calculations allowed to propose unconventional chloride-assisted mechanism of transfer hydrogenation to account for different behavior of 18e chloride complexes vs their less active 16e cationic counterparts. The key species initiating the catalytic cycle is the solvate complex [Cp*Rh(NPN)(iPrOH)]Cl, which does not result from direct coordination of iPrOH to 2a+PF6- rather forms via the Cl- dissociation in 1 promoted by specific interactions with alcohol, namely by H-bonding with the Cl ligand, Cp*Rh(NPN)Cl···HOR.
Добавил в систему: Кальсин Александр Михайлович

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