Abstract
The reaction mechanism of ester hydrogenation catalyzed by a bidentate aminophosphine ligated manganese catalyst was studied by DFT calculations. Particular emphasize was placed on the role of the alkoxide base additives. The presence of such basic promoters as KOtBu can improve the catalyst activity by lowering the activation barriers of H2 dissociation as well as the hydrogenation step. The promoting effect of KOtBu on H2 activation is much stronger than that of tert-butoxides with other alkali metals, which is crucial for the catalyst regeneration from the deactivated Mn-alkoxide species in the resting state.
Original language | English |
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Pages (from-to) | 136-143 |
Number of pages | 8 |
Journal | Journal of Catalysis |
Volume | 363 |
DOIs | |
Publication status | Published - 1 Jul 2018 |
Funding
This project has received funding from the European Research Council (ERC) under the European Union’s Horizon 2020 research and innovation programme (grant agreement No. 725686 ). P.O.K. acknowledges the partial support from the Government of the Russian Federation (Grant 08-08 ) and the Ministry of Education and Science of Russian Federation (Project 11.1706.2017/4.6). The authors thank the Netherlands Organization for Scientific Research (NWO) for the access to SurfSARA computational facilities. Appendix A
Keywords
- Ab initio thermodynamic analysis
- Catalyst deactivation
- DFT calculations
- Ester reduction
- Homogeneous catalysis
- Multifunctional catalysis
- Reaction mechanism