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The Malaprade reaction mechanism for ethylene glycol oxidation by periodic acid based on density functional theory (DFT)

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cris.lastimport.scopus2024-02-12T19:37:39Z
dc.abstract.enA general mechanism of the Malaprade oxidative carbon-carbon bond cleavage reaction of α-glycol in the presence of periodic acid has been proposed on the basis of density functional theory (DFT) computations. Ethylene glycol and periodic acid, both in their neutral forms, have been studied as noble substrate representatives in model reactions. The proposed reaction mechanism has been constructed based on and compared with previously published experimental kinetic, spectroscopic and temperature and pH-dependent studies. In the presented theoretical mechanistic considerations, four alternative molecular transformations have been analyzed from thermodynamic and kinetic points of view. Theoretically, the predicted activation energy barriers have been compared with experimental ones published elsewhere. The presented minimum energy pathway (MEP) unveiled the shape and conformation of the intermediate and transition state structures. The three-step reaction process involves the formation of a seven-membered quasi-ring assisted by an intramolecular hydrogen-bond intermediate structure forming one I-O bond (IC1_B), a cyclic ester intermediate forming two I-O bonds (IC2_C) and the final products formed at the two very last stages (HIO3, water and two formaldehyde molecules). The computed and energetically the most favourable reaction landscape proposed in this work uniforms and refines the mechanistic proposition given by Criegee for Malaprade type of reactions and further gives a detailed molecular understanding of the reaction rate and atomic connections en route the transformation. The molecular geometries of all stationary points (intermediate and transition state structures) lying on the potential energy hypersurface have been optimized at the four alternative DFT levels under the solvation model based on the density approximation: B3PW91, CAM-B3LYP, BMK, ωB97XD. The 6-311+G(2d,p) basis set for C, O, and H atoms and both the full (DGDZVP) and Ahlrichs-Weigend1 (def2-TZVP) basis sets for iodine atoms were used during the computations.
dc.affiliationUniwersytet Warszawski
dc.contributor.authorBłaziak, Kacper
dc.contributor.authorJezierska, Aneta
dc.contributor.authorPodgórniak, Kinga
dc.contributor.authorBłaziak, Mikołaj
dc.contributor.authorKołodziejczyk, Agata
dc.date.accessioned2024-01-26T10:27:33Z
dc.date.available2024-01-26T10:27:33Z
dc.date.copyright2023-08-04
dc.date.issued2023
dc.description.accesstimeAT_PUBLICATION
dc.description.financeŚrodki finansowe, o których mowa w art. 365 pkt. 2 ustawy
dc.description.number32
dc.description.versionFINAL_PUBLISHED
dc.description.volume25
dc.identifier.doi10.1039/D2CP04764K
dc.identifier.issn1463-9076
dc.identifier.urihttps://repozytorium.uw.edu.pl//handle/item/122658
dc.identifier.weblinkhttp://pubs.rsc.org/en/content/articlepdf/2023/CP/D2CP04764K
dc.languageeng
dc.pbn.affiliationchemical sciences
dc.relation.ispartofPhysical Chemistry Chemical Physics
dc.relation.pages21448-21455
dc.rightsCC-BY-NC
dc.sciencecloudnosend
dc.titleThe Malaprade reaction mechanism for ethylene glycol oxidation by periodic acid based on density functional theory (DFT)
dc.typeJournalArticle
dspace.entity.typePublication