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In Silico Olefin Metathesis with Ru-Based Catalysts Containing N-Heterocyclic Carbenes Bearing C60 Fullerenes

KGaA, Weinheim.Density functional theory calculations have been used to explore the potential of Ru-based complexes with 1,3-bis(2,4,6-trimethylphenyl)imidazolin-2-ylidene (SIMes) ligand backbone (A) being modified in silico by the insertion of a C60 molecule (B and C), as olefin metathesis catalysts. To this end, we investigated the olefin metathesis reaction catalyzed by complexes A, B, and C using ethylene as the substrate, focusing mainly on the thermodynamic stability of all possible reaction intermediates. Our results suggest that complex B bearing an electron-withdrawing N-heterocyclic carbene improves the performance of unannulated complex A. The efficiency of complex B is only surpassed by complex A when the backbone of the N-heterocyclic carbene of complex A is substituted by two amino groups. The particular performance of complexes B and C has to be attributed to electronic factors, that is, the electronic-donating capacity of modified SIMes ligand rather than steric effects, because the latter are predicted to be almost identical for complexes B and C when compared to those of A. Overall, this study indicates that such Ru-based complexes B and C might have the potential to be effective olefin metathesis catalysts

A.P. thanks the Spanish MINECO for a project CTQ2014-59832-JIN, and the European Commission for a Career Integration Grant (CIG09-GA-2011-293900)

© Chemistry - A European Journal, 2016, vol. 22, núm. 19, p. 6617-6623

Wiley

Manager: Ministerio de Economía y Competitividad (Espanya)
Author: Martínez López, Juan Pablo
Vummaleti, Sai Vikrama Chaitanya
Falivene, Laura
Nolan, Steven P.
Cavallo, Luigi
Solà i Puig, Miquel
Poater Teixidor, Albert
Date: 2016 May 4
Abstract: KGaA, Weinheim.Density functional theory calculations have been used to explore the potential of Ru-based complexes with 1,3-bis(2,4,6-trimethylphenyl)imidazolin-2-ylidene (SIMes) ligand backbone (A) being modified in silico by the insertion of a C60 molecule (B and C), as olefin metathesis catalysts. To this end, we investigated the olefin metathesis reaction catalyzed by complexes A, B, and C using ethylene as the substrate, focusing mainly on the thermodynamic stability of all possible reaction intermediates. Our results suggest that complex B bearing an electron-withdrawing N-heterocyclic carbene improves the performance of unannulated complex A. The efficiency of complex B is only surpassed by complex A when the backbone of the N-heterocyclic carbene of complex A is substituted by two amino groups. The particular performance of complexes B and C has to be attributed to electronic factors, that is, the electronic-donating capacity of modified SIMes ligand rather than steric effects, because the latter are predicted to be almost identical for complexes B and C when compared to those of A. Overall, this study indicates that such Ru-based complexes B and C might have the potential to be effective olefin metathesis catalysts
A.P. thanks the Spanish MINECO for a project CTQ2014-59832-JIN, and the European Commission for a Career Integration Grant (CIG09-GA-2011-293900)
Format: application/pdf
Citation: 025224
ISSN: 0947-6539 (versió paper)
1521-3765 (versió electrònica)
Document access: http://hdl.handle.net/10256/13300
Language: eng
Publisher: Wiley
Collection: MINECO/PE 2015-2018/CTQ2014-59832-JIN
Reproducció digital del document publicat a: http://dx.doi.org/10.1002/chem.201600383
Articles publicats (D-Q)
info:eu-repo/grantAgreement/EC/FP7/293900
Is part of: © Chemistry - A European Journal, 2016, vol. 22, núm. 19, p. 6617-6623
Rights: Tots els drets reservats
Subject: Funcional de densitat, Teoria del
Density functionals
Ful·lerens
Fullerenes
Metàtesi (Química)
Metathesis (Chemistry)
Ruteni
Ruthenium
Title: In Silico Olefin Metathesis with Ru-Based Catalysts Containing N-Heterocyclic Carbenes Bearing C60 Fullerenes
Type: info:eu-repo/semantics/article
Repository: DUGiDocs

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