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

Journal article (2018)

Authors

C. Liu ChemE/Inorganic Systems Engineering - AS
R. van Putten ChemE/Inorganic Systems Engineering - AS
Pavel O. Kulyaev ITMO University
G.A. Filonenko ChemE/Inorganic Systems Engineering - AS
E.A. Pidko ITMO University, ChemE/Algemeen
Research Group
ChemE/Inorganic Systems Engineering (AS) (TU Delft)
Copyright: © 2018 C. Liu, R. van Putten, Pavel O. Kulyaev, G.A. Filonenko, E.A. Pidko
DOI
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https://doi.org/10.1016/j.jcat.2018.04.018
Homogeneous catalysis Catalyst deactivation DFT calculations Reaction mechanism Ab initio thermodynamic analysis Ester reduction Multifunctional catalysis
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Published Date

2018

Language

English

Faculty

Applied Sciences

Department

ChemE/Chemical Engineering

Research Group

ChemE/Inorganic Systems Engineering

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.