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Understanding the Olefin Polymerization Initiation Mechanism by Cr(III)/SiO2 Using the Activation Strain Model

dc.contributor.authorNúñez-Zarur F
dc.contributor.authorComas-Vives A.
dc.date.accessioned2022-09-14T14:34:18Z
dc.date.available2022-09-14T14:34:18Z
dc.date.created2022
dc.identifier.issn19327447
dc.identifier.urihttp://hdl.handle.net/11407/7612
dc.descriptionIn this work, we computationally analyze the effect of the strain at the Cr(III) sites of a Cr(III)/SiO2 catalyst in the ethylene polymerization initiation considering two possible pathways: ethylene C–H activation and ethylene insertion into the Cr–O bond. We use the activation strain model (ASM), which dissects the activation energy of a reaction into strain and interaction energies, on a series of Cr(III) clusters with different sizes of the Si–O–Si rings. Our results indicate that more strained Cr(III) sites are more active than less strained ones and that the ethylene insertion into the Cr–O bond is more favorable than C–H bond activation for all sites. The ASM analysis reveals that the activation energies of both initiation mechanisms are dually controlled by interaction and strain energies. However, the comparison of the two mechanisms indicates that the preference for the ethylene insertion pathway is due to lower distortion of the ethylene fragment at the transition states, which is ultimately controlled by one intermolecular and one intramolecular interaction between the activated ethylene and the Cr(III) site fragments. © 2021 American Chemical Societyeng
dc.language.isoeng
dc.publisherAmerican Chemical Society
dc.relation.isversionofhttps://www.scopus.com/inward/record.uri?eid=2-s2.0-85122680473&doi=10.1021%2facs.jpcc.1c09753&partnerID=40&md5=5c78147761e822f789ba6a150a134583
dc.sourceJournal of Physical Chemistry C
dc.titleUnderstanding the Olefin Polymerization Initiation Mechanism by Cr(III)/SiO2 Using the Activation Strain Model
dc.typeArticle
dc.rights.accessrightsinfo:eu-repo/semantics/restrictedAccess
dc.publisher.programCiencias Básicas
dc.type.spaArtículo
dc.identifier.doi10.1021/acs.jpcc.1c09753
dc.subject.keywordActivation analysiseng
dc.subject.keywordActivation energyeng
dc.subject.keywordChromium compoundseng
dc.subject.keywordPolymerizationeng
dc.subject.keywordSiliconeng
dc.subject.keywordSilicon compoundseng
dc.subject.keywordActivation strain modeleng
dc.subject.keywordBond activationeng
dc.subject.keywordC-H bondeng
dc.subject.keywordDifferent sizeseng
dc.subject.keywordEthylene polymerizationeng
dc.subject.keywordInitiation mechanismeng
dc.subject.keywordInteraction energieseng
dc.subject.keywordModeling analyzeseng
dc.subject.keywordOlefins polymerizationseng
dc.subject.keyword]+ catalysteng
dc.subject.keywordEthyleneeng
dc.relation.citationvolume126
dc.relation.citationissue1
dc.relation.citationstartpage296
dc.relation.citationendpage308
dc.publisher.facultyFacultad de Ciencias Básicas
dc.affiliationNúñez-Zarur, F., Facultad de Ciencias Básicas, Universidad de Medellín, Carrera 87 No 30-65, Medellín, 050026, Colombia
dc.affiliationComas-Vives, A., Departament de Química, Universitat Autònoma de Barcelona, Bellaterra, Catalonia08193, Spain
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