Corrigendum to “Computational insights into the catalytic role of the base promoters in ester hydrogenation with homogeneous non-pincer-based Mn-P,N catalyst” [J. Catal. 363 (2018) 136–143]

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

doi:10.1016/j.jcat.2019.08.039

Cited by 5 publications

(6 citation statements)

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“…If polarities of the components of the solution are substantially different, non‐linear dependencies of free energies could be observed even for those steps, which do not involve the solvent molecules explicitly. 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 . 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: Resultssupporting

confidence: 65%

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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Section: Resultssupporting

confidence: 65%

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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“…Literature on 3d‐transition metals generally reports lower catalytic efficiencies, [30,48] which indicates that there is opportunity to maximize their potential towards sustainable catalyst systems. Catalysts based on 3d metals are known to be more prone to deactivation and formation of resting states, limiting their reactivity [4,50] …”

Section: Introductionmentioning

confidence: 99%

“…The activated catalyst is susceptible for potential deactivation/inhibition through the metal‐ligand cooperative addition of alcohol/water/base resulting in the formation of −OR adducts [54] . Alkoxide adduct of hydrogen donating alcohols such i ‐PrOH, MeOH and EtOH are often formed as intermediates in the course of catalytic hydrogenation reactions, and can even act as the resting states limiting the catalytic performance depending on their stability [50,55–60] . Competitive bonding of other species such as the solvent or the nucleophile base to the metal can slow down or even deactivate the catalyst.…”

Section: Introductionmentioning

confidence: 99%

Metal‐ligand cooperative activation of HX (X=H, Br, OR) bond on Mn based pincer complexes

Krieger

Sinha

Kalikadien

et al. 2021

Zeitschrift anorg allge chemie

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Reversible dissociation of H−X bond (M−L+H−X→M(X)‐L(H); ΔGHX ) is an important step during pre‐activation, catalysis and possible deactivation of acid‐base cooperative pincer based transition metal catalysts (M−L). Herein we carried out a high‐throughput computational investigation of the thermodynamic stability of different adducts in various functionalized Mn(I) based pincer complexes. We used a combination of density functional theory (DFT) and density functional tight binding (DFTB) calculations to analyze ΔGHX of >700 (M(X)‐L(H)) intermediates based on functionalized variants of four pincer type ligand scaffolds derived from PCP, CNC, PNP and SNS ligands. We discovered linear scaling relations between ΔGHX of various species. Strongest correlations were found between species of similar size and chemical nature e. g. ΔGtBuOH correlated best with ΔGiPrOH and worst with ΔGHBr . Such scaling relations can be useful for property based screening of catalysts and selection of (co)solvent/substrate/base for optimized reaction conditions. We also investigated the influence of the ligand backbone and the functionalization of donor and backbone sites in the ligand. Our analysis reveals the crucial role of the second coordination sphere functionalization for the reactivity of the complexes with impact in some cases exceeding that of the variation of the functional groups directly attached to the donor atoms.

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“…The same group later contributed computational insights into the reaction. [90] Clarke and co-workers also made an important contribution to the field with their complex 37 (seen in Scheme 14); this catalyst could reduce esters at particularly low catalyst loadings and reduce ketone asymmetrically to give secondary alcohols in high yield with enantiomeric excesses up to 97%. [91] Further developments from the group also include using the racemic version of 37 to reduce enantioenriched -chiral esters without a loss of stereochemistry.…”

Section: Accepted Manuscriptmentioning

confidence: 99%

The Rise of Manganese-Catalyzed Reduction Reactions

Schlichter

Werlé

2021

Synthesis

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Recent developments in manganese-catalyzed reducing transformations—hydrosilylation, hydroboration, hydrogenation, and transfer hydrogenation—are reviewed herein. Over the past half a decade (i.e., 2016-present), more than 115 research publications have been reported in these fields. Novel organometallic compounds and new reduction transformations have been discovered and further developed. Significant challenges that had historically acted as barriers for the use of manganese catalysts in reduction reactions are slowly being broken down. This review will hopefully assist in developing this research with a clear and concise overview of the catalyst structures and substrate transformations published so far.

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Corrigendum to “Computational insights into the catalytic role of the base promoters in ester hydrogenation with homogeneous non-pincer-based Mn-P,N catalyst” [J. Catal. 363 (2018) 136–143]

Cited by 5 publications

References 0 publications

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

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

Metal‐ligand cooperative activation of HX (X=H, Br, OR) bond on Mn based pincer complexes

The Rise of Manganese-Catalyzed Reduction Reactions

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