Propene hydroformylation reaction catalyzed by HRh(CO)(BISBI): a thermodynamic and kinetic analysis of the full catalytic cycle

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dc.creatorDaniel Herculano Cruz Neto
dc.creatorArtur Amasai Melo dos Santos
dc.creatorJúlio Cosme Santos da Silva
dc.creatorWillian Ricardo Rocha
dc.creatorRoberta Pereira Dias
dc.date.accessioned2023-02-23T18:41:28Z
dc.date.accessioned2025-09-08T23:13:20Z
dc.date.available2023-02-23T18:41:28Z
dc.date.issued2020
dc.description.sponsorshipCNPq - Conselho Nacional de Desenvolvimento Científico e Tecnológico
dc.description.sponsorshipFAPEMIG - Fundação de Amparo à Pesquisa do Estado de Minas Gerais
dc.description.sponsorshipFACEPE - Fundação de Apoio à Cultura, Ensino, Pesquisa e Extensão de Alfenas
dc.identifier.doihttps://doi.org/10.1002/ejic.202000799
dc.identifier.issn1099-0682
dc.identifier.urihttps://hdl.handle.net/1843/50330
dc.languageeng
dc.publisherUniversidade Federal de Minas Gerais
dc.rightsAcesso Restrito
dc.subjectQuímica inorgânica
dc.subjectCinética química
dc.subjectCatálise
dc.subjectTermodinâmica
dc.subjectRódio
dc.subjectFuncionais de densidade
dc.subjectCatalisadores de metais de transição
dc.subjectCompostos organometálicos
dc.subject.otherRhodium
dc.subject.otherHydroformylation
dc.subject.otherHomogeneous catalysis
dc.subject.otherKinetic analysis
dc.subject.otherDensity functional calculations
dc.titlePropene hydroformylation reaction catalyzed by HRh(CO)(BISBI): a thermodynamic and kinetic analysis of the full catalytic cycle
dc.typeArtigo de periódico
local.citation.epage3916
local.citation.issue41
local.citation.spage3907
local.citation.volume2020
local.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.
local.identifier.orcidhttps://orcid.org/0000-0002-5987-9369
local.identifier.orcidhttps://orcid.org/0000-0001-6368-492X
local.identifier.orcidhttps://orcid.org/0000-0002-0025-2158
local.identifier.orcidhttps://orcid.org/0000-0002-9473-7323
local.publisher.countryBrasil
local.publisher.departmentICX - DEPARTAMENTO DE QUÍMICA
local.publisher.initialsUFMG
local.url.externahttps://chemistry-europe.onlinelibrary.wiley.com/doi/10.1002/ejic.202000799

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