In Silico Olefin Metathesis with Ru-Based Catalysts Containing N-Heterocyclic Carbenes Bearing C60Fullerenes

Handle URI:
http://hdl.handle.net/10754/621699
Title:
In Silico Olefin Metathesis with Ru-Based Catalysts Containing N-Heterocyclic Carbenes Bearing C60Fullerenes
Authors:
Martínez, Juan Pablo; Vummaleti, Sai V. C. ( 0000-0001-7276-2475 ) ; Falivene, Laura ( 0000-0003-1509-6191 ) ; Nolan, Steven P.; Cavallo, Luigi ( 0000-0002-1398-338X ) ; Solà, Miquel ( 0000-0002-1917-7450 ) ; Poater, Albert ( 0000-0002-8997-2599 )
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. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
KAUST Department:
KAUST Catalysis Center (KCC); Physical Sciences and Engineering (PSE) Division
Citation:
Martínez 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.
Publisher:
Wiley-Blackwell
Journal:
Chemistry - A European Journal
Issue Date:
10-Apr-2016
DOI:
10.1002/chem.201600383
PubMed ID:
27059290
Type:
Article
ISSN:
0947-6539
Sponsors:
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). 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.).
Appears in Collections:
Articles; Physical Sciences and Engineering (PSE) Division; KAUST Catalysis Center (KCC)

Full metadata record

DC FieldValue Language
dc.contributor.authorMartínez, Juan Pabloen
dc.contributor.authorVummaleti, Sai V. C.en
dc.contributor.authorFalivene, Lauraen
dc.contributor.authorNolan, Steven P.en
dc.contributor.authorCavallo, Luigien
dc.contributor.authorSolà, Miquelen
dc.contributor.authorPoater, Alberten
dc.date.accessioned2016-11-03T13:23:02Z-
dc.date.available2016-11-03T13:23:02Z-
dc.date.issued2016-04-10en
dc.identifier.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.en
dc.identifier.issn0947-6539en
dc.identifier.pmid27059290-
dc.identifier.doi10.1002/chem.201600383en
dc.identifier.urihttp://hdl.handle.net/10754/621699-
dc.description.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.en
dc.description.sponsorshipA.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.).en
dc.publisherWiley-Blackwellen
dc.subjectDensity functional calculationsen
dc.subjectFullereneen
dc.subjectMetallacyclesen
dc.subjectMetathesisen
dc.subjectRutheniumen
dc.titleIn Silico Olefin Metathesis with Ru-Based Catalysts Containing N-Heterocyclic Carbenes Bearing C60Fullerenesen
dc.typeArticleen
dc.contributor.departmentKAUST Catalysis Center (KCC)en
dc.contributor.departmentPhysical Sciences and Engineering (PSE) Divisionen
dc.identifier.journalChemistry - A European Journalen
dc.contributor.institutionInstitut de Química Computacional i Catàlisi and Departament de Química; Universitat de Girona; Campus Montilivi 17071 Girona, Catalonia Spainen
dc.contributor.institutionDepartment of Inorganic and Physical Chemistry; Universiteit Gent; Krijgslaan 281 - S3 9000 Gent Belgiumen
dc.contributor.institutionChemistry Department; College of Science; King Saud University, P.O. Box 2455; Riyadh 11451 Saudi Arabiaen
kaust.authorVummaleti, Sai V. C.en
kaust.authorFalivene, Lauraen
kaust.authorCavallo, Luigien

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