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

Research output: Contribution to journal › Article › Academic › peer-review

42 Citations (Scopus)

164 Downloads (Pure)

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 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.

Original language	English
Pages (from-to)	136-143
Number of pages	8
Journal	Journal of Catalysis
Volume	363
DOIs	https://doi.org/10.1016/j.jcat.2018.04.018
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

Access to Document

10.1016/j.jcat.2018.04.018

Publishers VersionFinal published version, 1.88 MBLicence: CC BY

Cite this

@article{beeb4070d3134bd09a905f184071c7c5,

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.}",

year = "2018",

month = jul,

day = "1",

doi = "10.1016/j.jcat.2018.04.018",

language = "English",

volume = "363",

pages = "136--143",

journal = "Journal of Catalysis",

issn = "0021-9517",

publisher = "Academic Press Inc.",

}

TY - JOUR

T1 - Computational insights into the catalytic role of the base promoters in ester hydrogenation with homogeneous non-pincer-based Mn-P,N catalyst

AU - Liu, Chong

AU - van Putten, Robbert

AU - Kulyaev, Pavel O.

AU - Filonenko, Georgy A.

AU - Pidko, Evgeny A.

PY - 2018/7/1

Y1 - 2018/7/1

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

UR - http://www.scopus.com/inward/record.url?scp=85046668837&partnerID=8YFLogxK

U2 - 10.1016/j.jcat.2018.04.018

DO - 10.1016/j.jcat.2018.04.018

M3 - Article

AN - SCOPUS:85046668837

SN - 0021-9517

VL - 363

SP - 136

EP - 143

JO - Journal of Catalysis

JF - Journal of Catalysis

ER -

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

Abstract

Funding

Keywords

Access to Document

Other files and links

Fingerprint

Cite this