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Use este identificador para citar o ir al link de este elemento: http://hdl.handle.net/1843/50330
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Campo DCValorIdioma
dc.creatorDaniel Herculano Cruz Netopt_BR
dc.creatorArtur Amasai Melo dos Santospt_BR
dc.creatorJúlio Cosme Santos da Silvapt_BR
dc.creatorWillian Ricardo Rochapt_BR
dc.creatorRoberta Pereira Diaspt_BR
dc.date.accessioned2023-02-23T18:41:28Z-
dc.date.available2023-02-23T18:41:28Z-
dc.date.issued2020-
dc.citation.volume2020pt_BR
dc.citation.issue41pt_BR
dc.citation.spage3907pt_BR
dc.citation.epage3916pt_BR
dc.identifier.doihttps://doi.org/10.1002/ejic.202000799pt_BR
dc.identifier.issn1099-0682pt_BR
dc.identifier.urihttp://hdl.handle.net/1843/50330-
dc.description.resumoIn this article, full quantum mechanical calculations at the DFT-D level were carried out to study the full catalytic cycle for the hydroformylation of propene, catalyzed by the [HRh(CO)(BISBI)] catalyst. All intermediates and transition states along the elementary steps of the whole catalytic cycle were located and properly characterized. The kinetic constants calculated from transition state theory together with the application of the steady-state approximation were used to build a kinetic model for the hydroformylation reaction. The calculations show that regioselectivity of the reaction is set at the olefin insertion step, with the H2 oxidative addition being the rate-determining step of the entire cycle, with an activation energy of 26.0 kcal.mol-¹ for the linear pathway. The kinetic model showed that the CO gas acts as an inhibitor of the reaction at high pressure, and depending on the CO partial pressure, the rate of linear product formation is around 4 to 10 times faster. In line with experimental observations, our computational kinetic model indicated that at high CO partial pressures (> 40 atm), the HRh(CO)(BISBI) catalyst decreases its selectivity. Also was predicted from the computational kinetic model, that the reaction rates for both productions of normal and iso-butanal are less sensitive to effects of H2 partial pressure concerning the observed with the variation of the partial pressure of CO gas.pt_BR
dc.description.sponsorshipCNPq - Conselho Nacional de Desenvolvimento Científico e Tecnológicopt_BR
dc.description.sponsorshipFAPEMIG - Fundação de Amparo à Pesquisa do Estado de Minas Geraispt_BR
dc.description.sponsorshipFACEPE - Fundação de Apoio à Cultura, Ensino, Pesquisa e Extensão de Alfenaspt_BR
dc.languageengpt_BR
dc.publisherUniversidade Federal de Minas Geraispt_BR
dc.publisher.countryBrasilpt_BR
dc.publisher.departmentICX - DEPARTAMENTO DE QUÍMICApt_BR
dc.publisher.initialsUFMGpt_BR
dc.rightsAcesso Restritopt_BR
dc.subjectRhodiumpt_BR
dc.subjectHydroformylationpt_BR
dc.subjectHomogeneous catalysispt_BR
dc.subjectKinetic analysispt_BR
dc.subjectDensity functional calculationspt_BR
dc.subject.otherQuímica inorgânicapt_BR
dc.subject.otherCinética químicapt_BR
dc.subject.otherCatálisept_BR
dc.subject.otherTermodinâmicapt_BR
dc.subject.otherRódiopt_BR
dc.subject.otherFuncionais de densidadept_BR
dc.subject.otherCatalisadores de metais de transiçãopt_BR
dc.subject.otherCompostos organometálicospt_BR
dc.titlePropene hydroformylation reaction catalyzed by HRh(CO)(BISBI): a thermodynamic and kinetic analysis of the full catalytic cyclept_BR
dc.typeArtigo de Periódicopt_BR
dc.url.externahttps://chemistry-europe.onlinelibrary.wiley.com/doi/10.1002/ejic.202000799pt_BR
dc.identifier.orcidhttps://orcid.org/0000-0002-5987-9369pt_BR
dc.identifier.orcidhttps://orcid.org/0000-0001-6368-492Xpt_BR
dc.identifier.orcidhttps://orcid.org/0000-0002-0025-2158pt_BR
dc.identifier.orcidhttps://orcid.org/0000-0002-9473-7323pt_BR
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