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Composition- and Condition-Dependent Kinetics of Homogeneous Ester Hydrogenation by a Mn-Based Catalyst

[Image: see text] The reaction medium and conditions are the key parameters defining the efficiency and performance of a homogeneous catalyst. In the state-of-the-art molecular descriptions of catalytic systems by density functional theory (DFT) calculations, the reaction medium is commonly reduced...

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Autores principales: Krieger, Annika M., Kuliaev, Pavel, Armstrong Hall, Felix Q., Sun, Dapeng, Pidko, Evgeny A.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2020
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7735017/
https://www.ncbi.nlm.nih.gov/pubmed/33335641
http://dx.doi.org/10.1021/acs.jpcc.0c09953
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author Krieger, Annika M.
Kuliaev, Pavel
Armstrong Hall, Felix Q.
Sun, Dapeng
Pidko, Evgeny A.
author_facet Krieger, Annika M.
Kuliaev, Pavel
Armstrong Hall, Felix Q.
Sun, Dapeng
Pidko, Evgeny A.
author_sort Krieger, Annika M.
collection PubMed
description [Image: see text] The reaction medium and conditions are the key parameters defining the efficiency and performance of a homogeneous catalyst. In the state-of-the-art molecular descriptions of catalytic systems by density functional theory (DFT) calculations, the reaction medium is commonly reduced to an infinitely diluted ideal solution model. In this work, we carry out a detailed operando computational modeling analysis of the condition dependencies and nonideal solution effects on the mechanism and kinetics of a model ester hydrogenation reaction by a homogeneous Mn(I)-P,N catalyst. By combining DFT calculations, COSMO-RS solvent model, and the microkinetic modeling approach, the kinetic behavior of the multicomponent homogeneous catalyst system under realistic reaction conditions was investigated in detail. The effects of the reaction medium and its dynamic evolution in the course of the reaction were analyzed by comparing the results obtained for the model methyl acetate hydrogenation reaction in a THF solution and under solvent-free neat reaction conditions. The dynamic representations of the reaction medium give rise to strongly nonlinear effects in the kinetic models. The nonideal representation of the reaction medium results in pronounced condition dependencies of the computed energetics of the elementary reaction steps and the computed kinetic profiles but affects only slightly such experimentally accessible kinetic descriptors as the apparent activation energy and the degree of rate control.
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spelling pubmed-77350172020-12-15 Composition- and Condition-Dependent Kinetics of Homogeneous Ester Hydrogenation by a Mn-Based Catalyst Krieger, Annika M. Kuliaev, Pavel Armstrong Hall, Felix Q. Sun, Dapeng Pidko, Evgeny A. J Phys Chem C Nanomater Interfaces [Image: see text] The reaction medium and conditions are the key parameters defining the efficiency and performance of a homogeneous catalyst. In the state-of-the-art molecular descriptions of catalytic systems by density functional theory (DFT) calculations, the reaction medium is commonly reduced to an infinitely diluted ideal solution model. In this work, we carry out a detailed operando computational modeling analysis of the condition dependencies and nonideal solution effects on the mechanism and kinetics of a model ester hydrogenation reaction by a homogeneous Mn(I)-P,N catalyst. By combining DFT calculations, COSMO-RS solvent model, and the microkinetic modeling approach, the kinetic behavior of the multicomponent homogeneous catalyst system under realistic reaction conditions was investigated in detail. The effects of the reaction medium and its dynamic evolution in the course of the reaction were analyzed by comparing the results obtained for the model methyl acetate hydrogenation reaction in a THF solution and under solvent-free neat reaction conditions. The dynamic representations of the reaction medium give rise to strongly nonlinear effects in the kinetic models. The nonideal representation of the reaction medium results in pronounced condition dependencies of the computed energetics of the elementary reaction steps and the computed kinetic profiles but affects only slightly such experimentally accessible kinetic descriptors as the apparent activation energy and the degree of rate control. American Chemical Society 2020-11-24 2020-12-10 /pmc/articles/PMC7735017/ /pubmed/33335641 http://dx.doi.org/10.1021/acs.jpcc.0c09953 Text en © 2020 American Chemical Society This is an open access article published under a Creative Commons Non-Commercial No Derivative Works (CC-BY-NC-ND) Attribution License (http://pubs.acs.org/page/policy/authorchoice_ccbyncnd_termsofuse.html) , which permits copying and redistribution of the article, and creation of adaptations, all for non-commercial purposes.
spellingShingle Krieger, Annika M.
Kuliaev, Pavel
Armstrong Hall, Felix Q.
Sun, Dapeng
Pidko, Evgeny A.
Composition- and Condition-Dependent Kinetics of Homogeneous Ester Hydrogenation by a Mn-Based Catalyst
title Composition- and Condition-Dependent Kinetics of Homogeneous Ester Hydrogenation by a Mn-Based Catalyst
title_full Composition- and Condition-Dependent Kinetics of Homogeneous Ester Hydrogenation by a Mn-Based Catalyst
title_fullStr Composition- and Condition-Dependent Kinetics of Homogeneous Ester Hydrogenation by a Mn-Based Catalyst
title_full_unstemmed Composition- and Condition-Dependent Kinetics of Homogeneous Ester Hydrogenation by a Mn-Based Catalyst
title_short Composition- and Condition-Dependent Kinetics of Homogeneous Ester Hydrogenation by a Mn-Based Catalyst
title_sort composition- and condition-dependent kinetics of homogeneous ester hydrogenation by a mn-based catalyst
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7735017/
https://www.ncbi.nlm.nih.gov/pubmed/33335641
http://dx.doi.org/10.1021/acs.jpcc.0c09953
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