Computational insights into the catalytic role of the base promoters in ester hydrogenation with homogeneous non-pincer-based Mn-P,N catalyst

Chong Liu; Robbert van Putten; Pavel O. Kulyaev; Georgy A. Filonenko; Evgeny A. Pidko

doi:10.1016/j.jcat.2018.04.018

Computational insights into the catalytic role of the base promoters in ester hydrogenation with homogeneous non-pincer-based Mn-P,N catalyst

Chong Liu, Robbert van Putten, Pavel O. Kulyaev, Georgy A. Filonenko, Evgeny A. Pidko

Inorganic Materials & Catalysis

Onderzoeksoutput: Bijdrage aan tijdschrift › Tijdschriftartikel › Academic › peer review

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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 KO^tBu can improve the catalyst activity by lowering the activation barriers of H₂ dissociation as well as the hydrogenation step. The promoting effect of KO^tBu 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.

Originele taal-2	Engels
Pagina's (van-tot)	136-143
Aantal pagina's	8
Tijdschrift	Journal of Catalysis
Volume	363
DOI's	https://doi.org/10.1016/j.jcat.2018.04.018
Status	Gepubliceerd - 1 jul. 2018

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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

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title = "Computational insights into the catalytic role of the base promoters in ester hydrogenation with homogeneous non-pincer-based Mn-P,N catalyst",

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.",

keywords = "Ab initio thermodynamic analysis, Catalyst deactivation, DFT calculations, Ester reduction, Homogeneous catalysis, Multifunctional catalysis, Reaction mechanism",

author = "Chong Liu and {van Putten}, Robbert and Kulyaev, {Pavel O.} and Filonenko, {Georgy A.} and Pidko, {Evgeny A.}",

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AU - Liu, Chong

AU - van Putten, Robbert

AU - Kulyaev, Pavel O.

AU - Filonenko, Georgy A.

AU - Pidko, Evgeny A.

PY - 2018/7/1

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N2 - 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.

AB - 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.

KW - Ab initio thermodynamic analysis

KW - Catalyst deactivation

KW - DFT calculations

KW - Ester reduction

KW - Homogeneous catalysis

KW - Multifunctional catalysis

KW - Reaction mechanism

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Computational insights into the catalytic role of the base promoters in ester hydrogenation with homogeneous non-pincer-based Mn-P,N catalyst

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