Microkinetic Molecular Volcano Plots for Enhanced Catalyst Selectivity and Activity Predictions

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(13), P. 9829 - 9839

Published: June 17, 2024

Molecular volcano plots, which facilitate the rapid prediction of activity and selectivity prospective catalysts, have emerged as powerful tools for computational catalysis. Here, we integrate microkinetic modeling into plot framework to develop "microkinetic molecular plots". The resulting unified allows influence important reaction parameters, including temperature, time, concentration, be quickly incorporated more complex situations, such off-cycle resting states coupled catalytic cycles, tackled. Compared previous generations volcanoes, these counterparts offer a comprehensive understanding behavior, in product ratios can explicitly determined by tracking evolution each concentration over time. This is demonstrated examining two case studies, rhodium-catalyzed hydroformylation metal-catalyzed hydrosilylation, unique insights provided modeling, well ability simultaneously screen catalysts conditions, are highlighted. To construction plots/maps, introduce

Language: Английский

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Toward De Novo Catalyst Discovery: Fast Identification of New Catalyst Candidates for Alcohol‐Mediated Morita–Baylis–Hillman Reactions**

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(49)

Published: Oct. 13, 2023

Recently we have demonstrated how a genetic algorithm (GA) starting from random tertiary amines can be used to discover new and efficient catalyst for the alcohol-mediated Morita-Baylis-Hillman (MBH) reaction. In particular, discovered was shown experimentally eight times more active than DABCO, commonly catalyze MBH This represents breakthrough in using generative models optimization. However, GA procedure, hence discovery, relied on two important pieces of information; 1) knowledge that reaction 2) mechanism profile catalyzed reaction, particular transition state structure rate-determining step. Thus, truly de novo discovery must include these steps. Here present such method discovering candidates specific while simultaneously proposing We show phosphines are potential catalysts by screening 11 molecular templates representing common functional groups. The relies an automated workflow meta-dynamics calculations. Combining this candidate with our GA-based optimization results discovery.

Language: Английский

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Toward De Novo Catalyst Discovery: Fast Identification of New Catalyst Candidates for Alcohol‐Mediated Morita–Baylis–Hillman Reactions**

Angewandte Chemie, Journal Year: 2023, Volume and Issue: 135(49)

Published: Oct. 13, 2023

Abstract Recently we have demonstrated how a genetic algorithm (GA) starting from random tertiary amines can be used to discover new and efficient catalyst for the alcohol‐mediated Morita–Baylis–Hillman (MBH) reaction. In particular, discovered was shown experimentally eight times more active than DABCO, commonly catalyze MBH This represents breakthrough in using generative models optimization. However, GA procedure, hence discovery, relied on two important pieces of information; 1) knowledge that reaction 2) mechanism profile catalyzed reaction, particular transition state structure rate‐determining step. Thus, truly de novo discovery must include these steps. Here present such method discovering candidates specific while simultaneously proposing We show phosphines are potential catalysts by screening 11 molecular templates representing common functional groups. The relies an automated workflow meta‐dynamics calculations. Combining this candidate with our GA‐based optimization results discovery.

Language: Английский

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Computational unraveling of the effect of the positioning groups of Ir(III) complexes on catalytic activity

Tetrahedron, Journal Year: 2024, Volume and Issue: 153, P. 133852 - 133852

Published: Feb. 1, 2024

Language: Английский

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Convenient partial reduction of CO2 to a useful C1 building block: efficient access to 13C‐labelled N‐heterocyclic carbenes

ChemCatChem, Journal Year: 2024, Volume and Issue: unknown

Published: Oct. 8, 2024

Abstract The selective, transition metal‐free hydrosilylation of CO 2 to CH (OSiEt 3 ) has been achieved under mild conditions and in high isolated yields (up 90%) by using Et SiH the simple, easily prepared borohydride catalyst Li + [HB(C 6 F 5 ] − . resulting ‐derived bis(silyl)acetal product—whose mechanism formation interrogated through detailed computational experimental studies—can be rapidly valorized facile synthesis N ‐heterocyclic carbenes, via their corresponding imidazolium salts. By relatively inexpensive, isotopically enriched 13 this protocol can exploited prepare NHC isotopologues that are selectively C labelled at key, ligating C2 position. This provides an electronically responsive NMR spectroscopic handle with dramatically enhanced sensitivity, which directly benefit reactivity studies both organo‐ organometallic catalysis, where use is ubiquitous.

Language: Английский

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