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Authordc.contributor.authorParedes Gil, Katherine 
Authordc.contributor.authorMendizábal Emaldía, Fernando 
Authordc.contributor.authorJaque, Pablo 
Admission datedc.date.accessioned2019-10-22T03:11:15Z
Available datedc.date.available2019-10-22T03:11:15Z
Publication datedc.date.issued2019
Cita de ítemdc.identifier.citationJournal of Molecular Modeling (2019) 25: 305
Identifierdc.identifier.issn09485023
Identifierdc.identifier.other10.1007/s00894-019-4150-0
Identifierdc.identifier.urihttps://repositorio.uchile.cl/handle/2250/171895
Abstractdc.description.abstractThe chemical reactivity of the first- and second-generation Grubbs catalysts has always been a significant issue in olefin metathesis. In the present work, we study the [2+2] cycloreversion/cycloaddition and the alkylidene rotation involved into the interconversion of the ruthenacyclobutane intermediate, through the reaction force and reaction force constant analysis. It has been found that the structural contribution controls the barrier energy in the interconversion of ruthenacyclobutane via [2+2] cycloreversion/cycloaddition, which is slightly lower in the second generation of Grubbs catalysts while its electronic contribution is slightly higher, which unveils a major rigidity and donor/acceptor properties of the NHC. This finding explains a greater structural contribution in the rate constant. Moreover, on the basis of the reaction force constant, the process can be classified as “two-stage”-concerted reactions, noting a more asynchronous process when the first generation is used as a catalyst. Finally, a similar analysis into the alkylidene rotation was performed. It was determined that [2+2] cycloreversion and alkylidene rotations take place in a sequential manner, the energy barrier is again controlled by structural reorganization, and the pathway is less asynchronous.
Lenguagedc.language.isoen
Publisherdc.publisherNLM (Medline)
Type of licensedc.rightsAttribution-NonCommercial-NoDerivs 3.0 Chile
Link to Licensedc.rights.urihttp://creativecommons.org/licenses/by-nc-nd/3.0/cl/
Sourcedc.sourceJournal of molecular modeling
Keywordsdc.subjectDensity functional calculations
Keywordsdc.subjectGrubbs catalysts
Keywordsdc.subjectReaction force constant
Keywordsdc.subjectRu-centered [2+2] cycloreversion/cycloaddition
Títulodc.titleFurther understanding of the Ru-centered [2+2] cycloreversion/cycloaddition involved into the interconversion of ruthenacyclobutane using the Grubbs catalysts from a reaction force analysis
Document typedc.typeArtículo de revista
Catalogueruchile.catalogadorlaj
Indexationuchile.indexArtículo de publicación SCOPUS
uchile.cosechauchile.cosechaSI


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Attribution-NonCommercial-NoDerivs 3.0 Chile
Except where otherwise noted, this item's license is described as Attribution-NonCommercial-NoDerivs 3.0 Chile