title: In Silico Olefin Metathesis with Ru-Based Catalysts Containing N-Heterocyclic Carbenes Bearing C60 Fullerenes.
abstract: 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.
authors.affiliation: Institut de Química Computacional i Catàlisi and Departament de Química, Universitat de Girona, Campus Montilivi, 17071, Girona, Catalonia, Spain.
authors.forename: Juan Pablo
authors.initials: JP
authors.lastname: Martínez
authors.affiliation: KAUST Catalysis Center, Physical Sciences and Engineering Division, King Abdullah University of Science and Technology, Thuwal, 23955-6900, Saudi Arabia.
authors.forename: Sai Vikrama Chaitanya
authors.initials: SV
authors.lastname: Vummaleti
authors.affiliation: KAUST Catalysis Center, Physical Sciences and Engineering Division, King Abdullah University of Science and Technology, Thuwal, 23955-6900, Saudi Arabia.
authors.forename: Laura
authors.initials: L
authors.lastname: Falivene
authors.affiliation: Department of Inorganic and Physical Chemistry, Universiteit Gent, Krijgslaan 281 - S3, 9000, Gent, Belgium.|Chemistry Department, College of Science, King Saud University, P.O. Box 2455, Riyadh, 11451, Saudi Arabia.
authors.forename: Steven P
authors.initials: SP
authors.lastname: Nolan
authors.affiliation: KAUST Catalysis Center, Physical Sciences and Engineering Division, King Abdullah University of Science and Technology, Thuwal, 23955-6900, Saudi Arabia.
authors.forename: Luigi
authors.initials: L
authors.lastname: Cavallo
authors.affiliation: Institut de Química Computacional i Catàlisi and Departament de Química, Universitat de Girona, Campus Montilivi, 17071, Girona, Catalonia, Spain.
authors.forename: Miquel
authors.identifier: http://orcid.org/0000-0002-1917-7450
authors.initials: M
authors.lastname: Solà
authors.affiliation: Institut de Química Computacional i Catàlisi and Departament de Química, Universitat de Girona, Campus Montilivi, 17071, Girona, Catalonia, Spain. albert.poater@udg.edu.
authors.forename: Albert
authors.identifier: http://orcid.org/0000-0002-8997-2599
authors.initials: A
authors.lastname: Poater
keywords: density functional calculations; fullerene; metallacycles; metathesis; ruthenium