Weber, S., Brünig, J., Veiros, L. F., & Kirchner, K. (2021). Manganese-Catalyzed Hydrogenation of Ketones under Mild and Base-free Conditions. Organometallics, 40(9), 1388–1394. https://doi.org/10.1021/acs.organomet.1c00161
E163-01-1 - Forschungsgruppe Organometallische Chemie und Katalyse E163-03-5 - Forschungsgruppe Nachhaltige organische Synthese und Katalyse
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Journal:
Organometallics
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ISSN:
0276-7333
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Date (published):
10-May-2021
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Number of Pages:
7
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Publisher:
AMER CHEMICAL SOC
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Peer reviewed:
Yes
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Keywords:
Inorganic Chemistry; Physical and Theoretical Chemistry; Organic Chemistry
en
Abstract:
In this paper, several Mn(I) complexes were applied as catalysts for the homogeneous hydrogenation of ketones. The most active precatalyst is the bench-stable alkyl bisphosphine Mn(I) complex fac-[Mn(dippe) (CO)₃(CH₂CH₂CH₃)]. The reaction proceeds at room temperature under base-free conditions with a catalyst loading of 3 mol % and a hydrogen pressure of 10 bar. A temperature-dependent selectivity for the reduction of α,β-unsaturated carbonyls was observed. At room temperature, the carbonyl group was selectively hydrogenated, while the C═C bond stayed intact. At 60 °C, fully saturated systems were obtained. A plausible mechanism based on DFT calculations which involves an inner-sphere hydride transfer is proposed.
