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

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

doi:10.1016/j.jcat.2018.04.018

Cited by 43 publications

(38 citation statements)

References 35 publications

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“…Supporting DFT studies commonly focus on the analysis of the reactivity of the main catalytic complex, and little attention is often devoted toward the mechanistic role of the promoting substances that are necessary to achieve practical catalytic runs. The role of the base promotor was investigated in detail in ref (311). It was shown that the base promotor can play an important mechanistic role in facilitating key reaction steps, but more importantly, the presence of the base substantially influences the solvent properties and activities of key reaction components affecting thus dramatically the predicted free energy profiles (Figure 4).…”

Section: Mechanistic Complexity In Catalysis By 3d Transition Metalsmentioning

confidence: 99%

“…Key reaction steps of the catalytic ester hydrogenation by a Mn-P,N homogeneous catalyst, and the respective reaction free energy changes showing a strong nonlinear dependency of the thermodynamic parameters on the composition of the reaction mixture (base concentration). The graph presents a comparison of the free energy changes at the reaction conditions (373 K and 50 bar H 2 ) computed using the implicit PCM method for THF solvent (PCM THF ) and the combination of concentration-dependent FES with realistic COSMO-RS model that account for such effects as hydrogen solubility, change of solvent properties as a function of the composition of the reaction medium, presence of promotors, and other components of the system (data from ref (311)).…”

Section: Mechanistic Complexity In Catalysis By 3d Transition Metalsmentioning

confidence: 99%

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Computational Approach to Molecular Catalysis by 3d Transition Metals: Challenges and Opportunities

et al. 2018

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Computational chemistry provides a versatile toolbox for studying mechanistic details of catalytic reactions and holds promise to deliver practical strategies to enable the rational in silico catalyst design. The versatile reactivity and nontrivial electronic structure effects, common for systems based on 3d transition metals, introduce additional complexity that may represent a particular challenge to the standard computational strategies. In this review, we discuss the challenges and capabilities of modern electronic structure methods for studying the reaction mechanisms promoted by 3d transition metal molecular catalysts. Particular focus will be placed on the ways of addressing the multiconfigurational problem in electronic structure calculations and the role of expert bias in the practical utilization of the available methods. The development of density functionals designed to address transition metals is also discussed. Special emphasis is placed on the methods that account for solvation effects and the multicomponent nature of practical catalytic systems. This is followed by an overview of recent computational studies addressing the mechanistic complexity of catalytic processes by molecular catalysts based on 3d metals. Cases that involve noninnocent ligands, multicomponent reaction systems, metal–ligand and metal–metal cooperativity, as well as modeling complex catalytic systems such as metal–organic frameworks are presented. Conventionally, computational studies on catalytic mechanisms are heavily dependent on the chemical intuition and expert input of the researcher. Recent developments in advanced automated methods for reaction path analysis hold promise for eliminating such human-bias from computational catalysis studies. A brief overview of these approaches is presented in the final section of the review. The paper is closed with general concluding remarks.

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Section: Mechanistic Complexity In Catalysis By 3d Transition Metalsmentioning

confidence: 99%

Section: Mechanistic Complexity In Catalysis By 3d Transition Metalsmentioning

confidence: 99%

Computational Approach to Molecular Catalysis by 3d Transition Metals: Challenges and Opportunities

et al. 2018

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“…This has earlier been observed for the catalytic ester hydrogenation with Mn-PN in the presence of KO t Bu base and THF as the main solvent. [40] Similar to the partial-pressure dependencies discussed above, the variation of the DBU base concentration allows establishing the reaction conditions, at which the thermodynamic curves of the Catalysis and D2 deactivation of the Ru-CNC intersect.…”

Section: D1mentioning

confidence: 91%

Operando Modeling of Multicomponent Reactive Solutions in Homogeneous Catalysis: from Non‐standard Free Energies to Reaction Network Control

Kuliaev

Pidko

2019

ChemCatChem

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Dedicated to the memory of Prof. Georgy M. Zhidomirov.Optimization and execution of chemical reactions are to a large extend based on experience and chemical intuition of a chemist. The chemical intuition is rooted in the phenomenological Le Chatelier's principle that teaches us how to shift equilibrium by manipulating the reaction conditions. To access the underlying thermodynamic parameters and their conditiondependencies from the first principles is a challenge. Here, we present a theoretical approach to model non-standard free energies for a complex catalytic CO 2 hydrogenation system under operando conditions and identify the condition spaces where catalyst deactivation can potentially be suppressed. Investigation of the non-standard reaction free energy dependencies allows rationalizing the experimentally observed activity patterns and provides a practical approach to optimization of the reaction paths in complex multicomponent reactive catalytic systems.

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“…Recently Pidko et al. have suggested that t BuOK additive can play two roles . On one hand, K + cation can coordinate with both catalyst and substrate to polarize them and to bring them in proximity.…”

Section: Methodsmentioning

confidence: 99%

Design of Manganese Phenol Pi‐complexes as Shvo‐type Catalysts for Transfer Hydrogenation of Ketones

et al. 2019

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Catalytic hydrogenation is one of the most important reactions both in academic research and industry. We explored ability of the manganese pi‐complexes to act as Shvo‐type catalysts for transfer hydrogenation of ketones. DFT calculations suggested that the transfer of hydrogen atoms from the hypothetical intermediate [(C6Me3H2OH)Mn(CO)2H] to acetone has low activation barrier of 10.9 kcal mol−1. Experimentally a number of ketones with various functional groups (OMe, NH2, Cl, CF3, pyridyl) were successfully reduced in isopropanol at 90 °C in the presence of the complex [(C6Me3H2OH)Mn(CO)3]BF4 (1 mol %) and tBuOK (75 mol %). However, further investigation revealed that the reduction was mainly promoted by base rather than the manganese complex.

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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

Cited by 43 publications

References 35 publications

Computational Approach to Molecular Catalysis by 3d Transition Metals: Challenges and Opportunities

Computational Approach to Molecular Catalysis by 3d Transition Metals: Challenges and Opportunities

Operando Modeling of Multicomponent Reactive Solutions in Homogeneous Catalysis: from Non‐standard Free Energies to Reaction Network Control

Design of Manganese Phenol Pi‐complexes as Shvo‐type Catalysts for Transfer Hydrogenation of Ketones

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