Gawron, Martin and Gilch, Franziska and Schmidhuber, Daniel and Kelly, John A. and Downie, Thomas M. Horsley and von Wangelin, Axel Jacobi and Rehbein, Julia and Wolf, Robert (2024) Counterion Effect in Cobaltate-Catalyzed Alkene Hydrogenation. ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 63 (6): e202315381. ISSN 1433-7851, 1521-3773
Full text not available from this repository. (Request a copy)Abstract
We show that countercations exert a remarkable influence on the ability of anionic cobaltate salts to catalyze challenging alkene hydrogenations. An evaluation of the catalytic properties of [Cat][Co(eta(4)-cod)(2)] (Cat=K (1), Na (2), Li (3), ((Dep)nacnac)Mg (4), and N(Bu-n)(4) (5); cod=1,5-cyclooctadiene, (Dep)nacnac={2,6-Et2C6H3NC(CH3)}(2)CH)]) demonstrated that the lithium salt 3 and magnesium salt 4 drastically outperform the other catalysts. Complex 4 was the most active catalyst, which readily promotes the hydrogenation of highly congested alkenes under mild conditions. A plausible catalytic mechanism is proposed based on density functional theory (DFT) investigations. Furthermore, combined molecular dynamics (MD) simulation and DFT studies were used to examine the turnover-limiting migratory insertion step. The results of these studies suggest an active co-catalytic role of the counterion in the hydrogenation reaction through the coordination to cobalt hydride intermediates.
| Item Type: | Article |
|---|---|
| Uncontrolled Keywords: | HOMOGENEOUS HYDROGENATION; IRON CATALYSTS; OLEFIN; COMPLEXES; PRECATALYSTS; ARENES; LIGAND; CO; Alkenes; Cobalt; Homogenous Catalysis; Hydrogenation; Ion Pairing |
| Subjects: | 500 Science > 540 Chemistry & allied sciences |
| Divisions: | Chemistry and Pharmacy > Institut für Anorganische Chemie > Arbeitskreis Prof. Dr. Robert Wolf Chemistry and Pharmacy > Institut für Organische Chemie |
| Depositing User: | Dr. Gernot Deinzer |
| Date Deposited: | 17 Jul 2025 06:31 |
| Last Modified: | 17 Jul 2025 06:31 |
| URI: | https://pred.uni-regensburg.de/id/eprint/63529 |
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