Insights from Computational Studies on d
            <sup>0</sup>
            Metal‐Catalyzed Alkene and Alkyne Metathesis and Related Reactions

Solans‐Monfort, Xavier; Copéret, Christophe; Eisenstein, Odile

doi:10.1002/9783527674107.ch6

Cited by 4 publications

(2 citation statements)

References 105 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…This is achieved by comparing the energy profiles of the metallacyclobutane catalytic cycle over Re OMSs in USY with the absence/presence of a neighboring H + atom. It is noted that there have been extensive computational works on d 0 metal-catalyzed olefin metathesis reactions. − However, rarely did they consider the contribution from the nearby H + atom. The ReO x /USY model (T 192 O 384 , T = Si, Al) for calculations was built on the basis of the crystal structure model derived from SXRD and ND data.…”

Section: Results and Discussionmentioning

confidence: 99%

Rational Design of Synergistic Active Sites for Catalytic Ethene/2-Butene Cross-Metathesis in a Rhenium-Doped Y Zeolite Catalyst

Zhao

et al. 2021

ACS Catal.

View full text Add to dashboard Cite

Synthesizing atomically dispersed synergistic active pairs is crucial yet challenging in developing highly active heterogeneous catalysts for various industrially important reactions. Here, a single molecular Re species is immobilized on the inner surface of a Y zeolite with Brønsted acid sites (BASs) within atomic proximity to form Re OMS–BAS active pairs for the efficient catalysis of olefin metathesis reactions (OMS: olefin metathesis site). The synergy within the active pairs is revealed by studying the coadsorption geometry of the olefin substrates over the active pairs by synchrotron X-ray and neutron powder diffraction. It is shown that the BAS not only facilitates olefin adsorption but also aligns the olefin molecule to the Re OMS for efficient intermediate formation. Consequently, for the cross-metathesis of ethene and trans-2-butene to propene, this catalyst shows high activity under mild reaction conditions without observable deactivation. The catalyst outperforms not only traditional ReO x -based catalysts but also the best industrially applicable WO x -based catalyst thus far that we discovered previously. The concept of using two isolated active sites of different functionalities within atomic proximity in a confined cavity can provide opportunities for designing synergistically catalytic materials.

show abstract

Section: Results and Discussionmentioning

confidence: 99%

Rational Design of Synergistic Active Sites for Catalytic Ethene/2-Butene Cross-Metathesis in a Rhenium-Doped Y Zeolite Catalyst

Zhao

et al. 2021

ACS Catal.

View full text Add to dashboard Cite

show abstract

“…The general applicability of our proposed strategy for parameter optimization is then demonstrated for a realistic reaction, Mo-catalyzed olefin metathesis. 74 The mechanism of this reaction is well-known from QM calculations, 75,76 and hundreds of different catalysts have been reported in the literature. 77 The possibility of using a newly derived transition state force field to predict the stereoselectivity of alkene formation would be valuable for catalyst selection and design.…”

Section: Introductionmentioning

confidence: 99%

Development of a True Transition State Force Field from Quantum Mechanical Calculations

Madarász

Berta

Paton

2016

J. Chem. Theory Comput.

View full text Add to dashboard Cite

Transition state force fields (TSFF) treated the TS structure as an artificial minimum on the potential energy surface in the past decades. The necessary parameters were developed either manually or by the Quantum-to-molecular mechanics method (Q2MM). In contrast with these approaches, here we propose to model the TS structures as genuine saddle points at the molecular mechanics level. Different methods were tested on small model systems of general chemical reactions such as protonation, nucleophilic attack, and substitution, and the new procedure led to more accurate models than the Q2MM-type parametrization. To demonstrate the practicality of our approach, transferrable parameters have been developed for Mo-catalyzed olefin metathesis using quantum mechanical properties as reference data. Based on the proposed strategy, any force field can be extended with true transition state force field (TTSFF) parameters, and they can be readily applied in several molecular mechanics programs as well.

show abstract

From the Felkin‐Anh Rule to the Grignard Reaction: an Almost Circular 50 Year Adventure in the World of Molecular Structures and Reaction Mechanisms with Computational Chemistry**

Eisenstein

2022

Israel Journal of Chemistry

View full text Add to dashboard Cite

This rosarium article relates the adventure started 50 years ago of a computational chemist who was interested in molecules; what are they, what are their shape and how do they react. The story describes results, still valid today, obtained with highly simplified models of chemical reality and elementary computational methods and the gain resulting from the use of better models and more elaborate computational methods. It was necessary to select examples. In this presentation, focus is on hydride and dihydrogen complexes as well as on nucleophiles. Nucleophiles were considered as free hydrides in gas phase at the start of the rosarium while the Grignard reaction is treated with ab initio molecular mechanisms at the end of it.

show abstract

Insights from Computational Studies on d ⁰ Metal‐Catalyzed Alkene and Alkyne Metathesis and Related Reactions

Cited by 4 publications

References 105 publications

Rational Design of Synergistic Active Sites for Catalytic Ethene/2-Butene Cross-Metathesis in a Rhenium-Doped Y Zeolite Catalyst

Rational Design of Synergistic Active Sites for Catalytic Ethene/2-Butene Cross-Metathesis in a Rhenium-Doped Y Zeolite Catalyst

Development of a True Transition State Force Field from Quantum Mechanical Calculations

From the Felkin‐Anh Rule to the Grignard Reaction: an Almost Circular 50 Year Adventure in the World of Molecular Structures and Reaction Mechanisms with Computational Chemistry**

Contact Info

Product

Resources

About

Insights from Computational Studies on d 0 Metal‐Catalyzed Alkene and Alkyne Metathesis and Related Reactions

Cited by 4 publications

References 105 publications

Rational Design of Synergistic Active Sites for Catalytic Ethene/2-Butene Cross-Metathesis in a Rhenium-Doped Y Zeolite Catalyst

Rational Design of Synergistic Active Sites for Catalytic Ethene/2-Butene Cross-Metathesis in a Rhenium-Doped Y Zeolite Catalyst

Development of a True Transition State Force Field from Quantum Mechanical Calculations

From the Felkin‐Anh Rule to the Grignard Reaction: an Almost Circular 50 Year Adventure in the World of Molecular Structures and Reaction Mechanisms with Computational Chemistry**

Contact Info

Product

Resources

About

Insights from Computational Studies on d ⁰ Metal‐Catalyzed Alkene and Alkyne Metathesis and Related Reactions