Mechanistic diversity in acetophenone transfer hydrogenation catalyzed by ruthenium iminophosphonamide complexes
| Autor: | Rinaldo Poli, Tat'yana A. Peganova, Alexander M. Kalsin, Eric Deydier, Natalia V. Belkova, Iana S. Sinopalnikova, Ivan V. Fedyanin |
|---|---|
| Přispěvatelé: | A. N. Nesmeyanov Institute of Organoelement Compounds (INEOS), Russian Academy of Sciences [Moscow] (RAS), Laboratoire de chimie de coordination (LCC), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie de Toulouse (ICT-FR 2599), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut Universitaire de France (IUF), Ministère de l'Education nationale, de l’Enseignement supérieur et de la Recherche (M.E.N.E.S.R.), Russian Science Foundation (grant No. 19-13-00459), Ministry of Science and Higher Education of the Russian Federation, Institut de Chimie de Toulouse (ICT), Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS) |
| Rok vydání: | 2020 |
| Předmět: |
chemistry.chemical_classification
Ketone [CHIM.ORGA]Chemical Sciences/Organic chemistry 010405 organic chemistry Hydride Ligand Aryl chemistry.chemical_element [CHIM.CATA]Chemical Sciences/Catalysis 010402 general chemistry Transfer hydrogenation 01 natural sciences Medicinal chemistry 0104 chemical sciences Ruthenium Catalysis Inorganic Chemistry chemistry.chemical_compound chemistry [CHIM.COOR]Chemical Sciences/Coordination chemistry Acetophenone |
| Zdroj: | Dalton Transactions Dalton Transactions, Royal Society of Chemistry, 2020, 49 (5), pp.1473-1484. ⟨10.1039/c9dt04532e⟩ Dalton Transactions, 2020, 49 (5), pp.1473-1484. ⟨10.1039/c9dt04532e⟩ |
| ISSN: | 1477-9234 1477-9226 |
| DOI: | 10.1039/c9dt04532e |
| Popis: | International audience; 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 hydride and proton transfer assisted by the basic N-atom of the NPN ligand, which promotes catalysis via precoordination of an alcohol molecule by hydrogen bonding. |
| Databáze: | OpenAIRE |
| Externí odkaz: |
|