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dc.contributor.authorVicente Poutás, Luis Carlos de
dc.contributor.authorCastiñeira Reis, Marta
dc.contributor.authorSanz Díez, Roberto 
dc.contributor.authorSilva López, Carlos
dc.contributor.authorNieto Faza, Olalla .
dc.date.accessioned2016-11-21T08:04:24Z
dc.date.available2017-11-07T03:45:06Z
dc.date.issued2016-11
dc.identifier.issn0020-1669
dc.identifier.urihttp://hdl.handle.net/10259/4273
dc.description.abstractWe propose a novel mechanism for the deoxydehydration (DODH) reaction of glycols catalyzed by a [Bu4N][VO2(dipic)] complex (dipic = pyridine-2,6-dicarboxylate) using triphenylphosphine as a reducing agent. Using density functional theory, we have confirmed that the preferred sequence of reaction steps involves reduction of the V(V) complex by phosphine, followed by condensation of the glycol into a [VO(dipic)(-O-CH2CH2-O-)] V(III) complex (6), which then evolves to the alkene product, with recovery of the catalyst. In contrast to the usually invoked closed-shell mechanism for the latter steps, where 6 suffers a [3+2] retrocycloaddition, we have found that the homolytic cleavage of one of the C–O bonds in 6 is preferred by 12 kcal/mol. The resulting diradical intermediate then collapses to a metallacycle that evolves to the product through an aromatic [2+2] retrocycloaddition. We use this key change in the mechanism to propose ways to design better catalysts for this transformation. The analysis of the mechanisms in both singlet and triplet potential energy surfaces, together with the location of the MECPs between them, showcases this reaction as an interesting example of two-state reactivity.en
dc.description.sponsorshipXunta de Galicia and Ministerio de Economiá y Competitividad for funding through Projects EM2014/040 and CTQ2013-48937-C2-1-P and CTQ2013-48937-C2-2-P, respectively. R.S. thanks the Junta de Castilla y León for funding through projects BU237U13 and BU076U16.en
dc.format.mimetypeapplication/pdf
dc.language.isoenges
dc.publisherAmerican Chemical Societyen
dc.relation.ispartofInorganic chemistry, 2016, V. 5, n 21, p. 11372–11382en
dc.subject.otherChemistry, Organicen
dc.subject.otherQuímica orgánicaes
dc.titleA Radical Mechanism for the Vanadium-Catalyzed Deoxydehydration of Glycolsen
dc.typeinfo:eu-repo/semantics/article
dc.rights.accessRightsinfo:eu-repo/semantics/openAccess
dc.relation.publisherversionhttp://dx.doi.org/10.1021/acs.inorgchem.6b01916
dc.type.hasVersioninfo:eu-repo/semantics/acceptedVersionen


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