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dc.contributor.authorCambeiro Cambeiro, Fermín
dc.contributor.authorMartínez Núñez, Emilio
dc.contributor.authorVarela Carrete, Jesús Ángel
dc.contributor.authorSaá Rodríguez, Carlos
dc.date.accessioned2020-10-05T06:52:14Z
dc.date.available2020-10-05T06:52:14Z
dc.date.issued2015
dc.identifier.citationCambeiro, F., Martínez-Núñez, E., Varela, J. A., Saá, C. (2015). DFT and Kinetic Monte Carlo Study of TMS-Substituted Ruthenium Vinyl Carbenes: Key Intermediates for Stereoselective Cyclizations. ACS Catalysis, 5, 11, 6255-6262
dc.identifier.urihttp://hdl.handle.net/10347/23349
dc.descriptionNOTICE: This is the peer reviewed version of the following article: Cambeiro, F., Martínez-Núñez, E., Varela, J. A., Saá, C. (2015). DFT and Kinetic Monte Carlo Study of TMS-Substituted Ruthenium Vinyl Carbenes: Key Intermediates for Stereoselective Cyclizations. ACS Catalysis, 5, 11, 6255-6262. [doi: 10.1021/acscatal.5b01333]. This article may be used for non-commercial purposes in accordance with American Chemical Society Terms and Conditions for self-archiving
dc.description.abstractMechanistic pathways for the cyclization of 1,5-alkynylacetal with N2CHTMS in the presence of Cp- and Cp*RuCl(cod) to afford Z and E (trimethylsilyl)vinyl spiroacetals have been calculated. Calculations show the presence of three conformers in equilibrium for the initially formed ruthenium carbenes. Differences in the stabilities and reactivities of the conformers, depending on the use of a Cp- or Cp*-ruthenium catalyst, are responsible for the favorable active reaction pathways in each case, even though the geometry of the resulting product is the same regardless of the catalyst used. Kinetic Monte Carlo (KMC) simulations with rate coefficients, including tunneling probabilities for the hydride transfer step, were used to model the evolution of reactants, intermediates and products for all calculated pathways. It was shown that one path is almost exclusively active for each catalyst. Finally, the energetic span model of Kozuch and Shaik was used to calculate the energetic span (δE), the TOF-determining transition state (TDTS), the TOF-determining intermediate (TDI) and the TOF value for each of the feasible mechanistic pathways.
dc.description.sponsorshipThis work was supported by MICINN (Spain) (projects CTQ2011-28258 and CTQ2014-51912REDC), Xunta de Galicia, and the Euro-pean Regional Development Fund (projects GRC2014/032 and EM 2012/051). F.C. thanks XUGA for a predoctoral contract
dc.language.isoeng
dc.publisherAmerican Chemical Society
dc.relationinfo:eu-repo/grantAgreement/MINECO/Plan Estatal de Investigación Científica y Técnica y de Innovación 2013-2016/CTQ2014-51912/ES/RED ORFEO-CINQA "CENTRO DE INNOVACION EN QUIMICA AVANZADA”
dc.relationinfo:eu-repo/grantAgreement/MICINN/Plan Nacional de I+D+i 2008-2011/CTQ2011-28258/ES/CATALISIS ORGANOMETALICA: FUNCIONALIZACION DE ENLACES C-H
dc.rightsCopyright © 2015 American Chemical Society. This article may be used for non-commercial purposes in accordance with American Chemical Society Terms and Conditions for self-archiving
dc.subjectDensity functional calculations
dc.subjectEnergetic spam model
dc.subjectKinetic Monte Carlo simulations
dc.subjectRuthenium vinyl carbenes
dc.subjectTOF
dc.titleDFT and Kinetic Monte Carlo Study of TMS-Substituted Ruthenium Vinyl Carbenes: Key Intermediates for Stereoselective Cyclizations
dc.typeinfo:eu-repo/semantics/article
dc.identifier.DOI10.1021/acscatal.5b01333
dc.relation.publisherversionhttps://doi.org/10.1021/acscatal.5b01333
dc.type.versioninfo:eu-repo/semantics/acceptedVersion
dc.identifier.e-issn2155-5435
dc.rights.accessrightsinfo:eu-repo/semantics/openAccess
dc.contributor.affiliationUniversidade de Santiago de Compostela. Centro de Investigación en Química Biolóxica e Materiais Moleculares
dc.contributor.affiliationUniversidade de Santiago de Compostela. Departamento de Química Orgánica
dc.description.peerreviewedSI


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