In Silico Olefin Metathesis with Ru-Based Catalysts Containing N-Heterocyclic Carbenes Bearing C60Fullerenes
AuthorsMartínez, Juan Pablo
Vummaleti, Sai V. C.
Nolan, Steven P.
KAUST DepartmentChemical Science Program
KAUST Catalysis Center (KCC)
Physical Science and Engineering (PSE) Division
Online Publication Date2016-04-05
Print Publication Date2016-05-04
Permanent link to this recordhttp://hdl.handle.net/10754/621699
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AbstractDensity 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. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
CitationMartínez JP, Vummaleti SVC, Falivene L, Nolan SP, Cavallo L, et al. (2016) In Silico Olefin Metathesis with Ru-Based Catalysts Containing N-Heterocyclic Carbenes Bearing C60Fullerenes. Chem Eur J 22: 6617–6623. Available: http://dx.doi.org/10.1002/chem.201600383.
SponsorsA.P. thanks the Spanish MINECO for a project CTQ2014-59832-JIN, and the European Commission for a Career Integration Grant (CIG09-GA-2011-293900). L.C. and S.P.N thank King Abdullah University of Science and Technology (CCF project) for support. J.P.M. gratefully acknowledges the receipt of his Ph.D. fellowship (register/application number 217067/312543) financed by the Mexican CONACYT. This work has been also supported by the Ministerio de Economia y Competitividad (MINECO) of Spain (Project CTQ2014-54306-P) and the Generalitat de Catalunya (project number 2014SGR931, Xarxa de Referencia en Quimica Teorica i Computacional, and ICREA Academia 2014 prize for M.S.).
JournalChemistry - A European Journal
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