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dc.creatorCarrasco Carrasco, Carlos Jesúses
dc.creatorMontilla Ramos, Francisco Javieres
dc.creatorGalindo del Pozo, Agustínes
dc.date.accessioned2018-08-06T09:35:32Z
dc.date.available2018-08-06T09:35:32Z
dc.date.issued2018
dc.identifier.citationCarrasco Carrasco, C.J., Montilla Ramos, F.J. y Galindo del Pozo, A. (2018). Molybdenum-catalyzed enantioselective sulfoxidation controlled by a nonclassical hydrogen bond between coordinated chiral imidazolium-based dicarboxylate and peroxido ligands. Molecules, 23, 1595-1-1595-12.
dc.identifier.issn1420-3049es
dc.identifier.urihttps://hdl.handle.net/11441/77852
dc.description.abstractChiral alkyl aryl sulfoxides were obtained by molybdenum-catalyzed oxidation of alkyl aryl sulfides with hydrogen peroxide as oxidant in mild conditions with high yields and moderate enantioselectivities. The asymmetry is generated by the use of imidazolium-based dicarboxylic compounds, HLR. The in-situ-generated catalyst, a mixture of aqueous [Mo(O)(O2)2(H2O)n] with HLR as chirality inductors, in the presence of [PPh4]Br, was identified as the anionic binuclear complex [PPh4]{[Mo(O)(O2)2(H2O)]2( -LR)}, according to spectroscopic data and Density Functional Theory (DFT) calculations. A nonclassical hydrogen bond between one C–H bond of the alkyl R group of coordinated (LR)- and one oxygen atom of the peroxido ligand was identified as the interaction responsible for the asymmetry in the process. Additionally, the step that governs the enantioselectivity was theoretically analyzed by locating the transition states of the oxido-transfer to PhMeS of model complexes [Mo(O)(O2)2(H2O)( 1-O-LR)]- (R = H, iPr). The DDG6= is ca. 0 kcal mol-1 for R = H, racemic sulfoxide, meanwhile for chiral species the DDG6= of ca. 2 kcal mol-1 favors the formation of (R)-sulfoxide.es
dc.description.sponsorshipJunta de Andalucía (Proyecto de Excelencia FQM-7079)es
dc.description.sponsorshipUniversidad de Sevilla (VI Plan Propio)es
dc.formatapplication/pdfes
dc.language.isoenges
dc.publisherMDPIes
dc.relation.ispartofMolecules, 23, 1595-1-1595-12.
dc.rightsAttribution-NonCommercial-NoDerivatives 4.0 Internacional*
dc.rights.urihttp://creativecommons.org/licenses/by-nc-nd/4.0/*
dc.subjectSulfoxidationes
dc.subjectAsymmetric catalysises
dc.subjectMolybdenumes
dc.subjectHydrogen peroxidees
dc.subjectDensity Functional Theoryes
dc.titleMolybdenum-catalyzed enantioselective sulfoxidation controlled by a nonclassical hydrogen bond between coordinated chiral imidazolium-based dicarboxylate and peroxido ligandses
dc.typeinfo:eu-repo/semantics/articlees
dcterms.identifierhttps://ror.org/03yxnpp24
dc.type.versioninfo:eu-repo/semantics/publishedVersiones
dc.rights.accessRightsinfo:eu-repo/semantics/openAccesses
dc.contributor.affiliationUniversidad de Sevilla. Departamento de Química Inorgánicaes
dc.relation.projectIDFQM-7079es
dc.relation.publisherversionhttp://www.mdpi.com/1420-3049/23/7/1595/htmes
dc.identifier.doi10.3390/molecules23071595es
idus.format.extent12es
dc.journaltitleMoleculeses
dc.publication.volumen23es
dc.publication.initialPage1595-1es
dc.publication.endPage1595-12es
dc.contributor.funderJunta de Andalucía
dc.contributor.funderUniversidad de Sevilla

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