Ítem


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)

Wiley

Director: Ministerio de Economía y Competitividad (Espanya)
Autor: Martínez López, Juan Pablo
Vummaleti, Sai Vikrama Chaitanya
Falivene, Laura
Nolan, Steven P.
Cavallo, Luigi
Solà i Puig, Miquel
Poater Teixidor, Albert
Data: 4 maig 2016
Resum: 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
Accés al document: http://hdl.handle.net/10256/13300
Llenguatge: eng
Editor: Wiley
Col·lecció: info:eu-repo/semantics/altIdentifier/doi/10.1002/chem.201600383
info:eu-repo/semantics/altIdentifier/issn/0947-6539
info:eu-repo/semantics/altIdentifier/eissn/1521-3765
info:eu-repo/grantAgreement/MINECO//CTQ2014-59832-JIN/ES/ESCANEO COMPUTACIONAL DE RELACIONES ESTRUCTURA%2FACTIVIDAD DE CATALIZADORES DE OXIDACION DEL AGUA PARA LA GENERACION DE H2/
info:eu-repo/grantAgreement/EC/FP7/293900/EU/Ab initio Statics and Molecular Dynamics Simulation of Olefin Metathesis Catalysts for pharmacological purposes/COMPUTEDRUG
Drets: Tots els drets reservats
Matèria: Funcional de densitat, Teoria del
Density functionals
Ful·lerens
Fullerenes
Metàtesi (Química)
Metathesis (Chemistry)
Ruteni
Ruthenium
Títol: In Silico Olefin Metathesis with Ru-Based Catalysts Containing N-Heterocyclic Carbenes Bearing C60 Fullerenes
Tipus: info:eu-repo/semantics/article
Repositori: DUGiDocs

Matèries

Autors