Mechanisms of Formation of Hemiacetals: Intrinsic Reactivity Analysis

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dc.contributor.authorAzofra, Luis Miguel
dc.contributor.authorAlkorta, Ibon
dc.contributor.authorElguero, Jose
dc.contributor.authorToro Labbe, Alejandro
dc.date.accessioned2024-01-10T12:40:16Z
dc.date.available2024-01-10T12:40:16Z
dc.date.issued2012
dc.description.abstractThe reaction mechanism of the hemiacetal formation from formaldehyde and methanol has been studied theoretically at the B3LYP/6-311+ +G(d,p) level. In addition to the study of the reaction between the isolated reactants, three different kinds of catalysis have been explored. The first one examines the use of assistants, especially bridging water molecules, in the proton transfer process. The second one attempts to increase the local electrophilicity of the carbon atom in formaldehyde with the presence of a Bronsted acid (H+ or H3O+). The last one considers the combined effect of both catalytic strategies. The reaction force, the electronic chemical potential, and the reaction electronic flux have been characterized for the reaction path in each case. In general, it has been found that structural rearrangements represent an important energetic penalty during the activation process. The barriers for the reactions catalyzed by Bronsted acids show a high percentage of electronic reorganization contribution. The catalytic effects for the reactions assisted by water molecules are due to a reduction of the strain The reaction that includes both acid catalysis and proton assistance transfer shows the lowest in the transition state structures. energy barrier (25.0 kJ mol(-1)).
dc.description.funderMinisterio de Ciencia e Innovacion
dc.description.funderComunidad Autonoma de Madrid (Project MADRISO-LAR2)
dc.description.funderFONDECYT
dc.fechaingreso.objetodigital2024-04-23
dc.format.extent10 páginas
dc.fuente.origenWOS
dc.identifier.doi10.1021/jp304495f
dc.identifier.eissn1520-5215
dc.identifier.issn1089-5639
dc.identifier.pubmedidMEDLINE:22784613
dc.identifier.urihttps://doi.org/10.1021/jp304495f
dc.identifier.urihttps://repositorio.uc.cl/handle/11534/77291
dc.identifier.wosidWOS:000307264300017
dc.information.autorucQuímica;Toro A;S/I;99827
dc.issue.numero31
dc.language.isoen
dc.nota.accesocontenido parcial
dc.pagina.final8259
dc.pagina.inicio8250
dc.publisherAMER CHEMICAL SOC
dc.revistaJOURNAL OF PHYSICAL CHEMISTRY A
dc.rightsacceso restringido
dc.subjectREACTION ELECTRONIC FLUX
dc.subjectDOUBLE PROTON-TRANSFER
dc.subjectREACTION FORCE
dc.subjectSUGARS MUTAROTATION
dc.subjectCHEMICAL-REACTIONS
dc.subjectBASE CATALYSIS
dc.subjectACID
dc.subjectDENSITY
dc.subjectFORMALDEHYDE
dc.subjectENERGY
dc.subject.ods03 Good Health and Well-being
dc.subject.odspa03 Salud y bienestar
dc.titleMechanisms of Formation of Hemiacetals: Intrinsic Reactivity Analysis
dc.typeartículo
dc.volumen116
sipa.codpersvinculados99827
sipa.indexWOS
sipa.indexScopus
sipa.trazabilidadCarga SIPA;09-01-2024
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