Mechanism of the Manganese-Pincer-Catalyzed Acceptorless Dehydrogenative Coupling of Nitriles and Alcohols
dc.contributor.author
dc.date.accessioned
2019-03-21T12:18:16Z
dc.date.available
2019-03-21T12:18:16Z
dc.date.issued
2019-01-11
dc.identifier.issn
0002-7863
dc.identifier.uri
dc.description.abstract
A recent study showed that a Mn-pincer could catalyze the acceptorless dehydrogenative coupling of nitriles and alcohols to yield acrylonitriles. The reaction mechanism proposed in that work contained some intermediates that, in most of the cases, were not characterized. Moreover, one of the intermediates involved a charged separation, which is unlikely in apolar solvents. To clarify the reaction mechanism of this critical reaction, we decided to perform a DFT study. Our results prove the existence of a cooperative effect of the metal and the ligand in several steps of the catalytic cycle. We also find the presence of several equilibria between isomeric intermediates where water, or the same alcohol reagent, takes part in assisting the proton transfer. Furthermore, we have analyzed the charge-separated structure proposed experimentally and have found a nearly pure covalent bond between the two expected charged moieties. Finally, the Knoevenagel condensation step that generates the acrylonitrile is found to be the rate-determining step
dc.description.sponsorship
J.A.L.U. thanks the Universitat de Girona for the IFUdG2017 Ph.D. fellowship. A.P. and M.S. are grateful to the Ministerio de Economía y Competitividad (MINECO) of Spain (projects CTQ2014-59832-JIN and CTQ2017-85341-P), the Generalitat de Catalunya (project 2017SGR39, Xarxa de Referència en Quı́mica Teòrica i Computacional, the ICREA Academia prize 2014 awarded to M.S.), and the European Fund for Regional Development (FEDER) grant UNGI10-4E-801
dc.format.mimetype
application/pdf
dc.language.iso
eng
dc.publisher
American Chemical Society
dc.relation
info:eu-repo/grantAgreement/MINECO//CTQ2014-59832-JIN/ES/ESCANEO COMPUTACIONAL DE RELACIONES ESTRUCTURA%2FACTIVIDAD DE CATALIZADORES DE OXIDACION DEL AGUA PARA LA GENERACION DE H2/
info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2013-2016/CTQ2017-85341-P/ES/AVANCES EN LA REACTIVIDAD DE FULLERENOS Y NANOTUBOS: ESTUDIOS TEORICO-EXPERIMENTALES DE CICLACIONES CATALIZADAS POR METALES DE TRANSICION/
dc.relation.isformatof
Versió postprint del document publicat a: https://doi.org/10.1021/jacs.8b11308
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© Journal of the American Chemical Society, 2019, vol. 141, núm. 6, p. 2398-2403
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Articles publicats (D-Q)
dc.rights
Tots els drets reservats
dc.subject
dc.title
Mechanism of the Manganese-Pincer-Catalyzed Acceptorless Dehydrogenative Coupling of Nitriles and Alcohols
dc.type
info:eu-repo/semantics/article
dc.rights.accessRights
info:eu-repo/semantics/openAccess
dc.date.embargoEndDate
info:eu-repo/date/embargoEnd/2020-01-11
dc.type.version
info:eu-repo/semantics/acceptedVersion
dc.identifier.doi
dc.identifier.idgrec
029532
dc.contributor.funder
dc.type.peerreviewed
peer-reviewed
dc.relation.FundingProgramme
dc.relation.ProjectAcronym
dc.identifier.eissn
1520-5126