Please use this identifier to cite or link to this item: http://hdl.handle.net/10553/69301
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dc.contributor.authorAzofra Mesa, Luis Miguelen_US
dc.contributor.authorCavallo, Luigien_US
dc.date.accessioned2020-01-23T14:28:36Z-
dc.date.available2020-01-23T14:28:36Z-
dc.date.issued2019en_US
dc.identifier.issn1432-881Xen_US
dc.identifier.otherWoS-
dc.identifier.urihttp://hdl.handle.net/10553/69301-
dc.description.abstractIn this work, we study the potential catalytic role of previously identified Mn(I)-PNN complexes in the Claisen-Tishchenko reaction. An in-depth investigation of the reaction mechanism suggests that, after activation of the 16e pre-catalyst, a hydrogenated 18e active species is generated. Based on calculations, rate-limiting barriers in a range of ca. 15-20kcalmol(-1) are seen for a model process consisting in the esterification of acetaldehyde into ethyl acetate at 100 degrees C and 1atm reaction conditions (in toluene solution). Our hypothesis is centred on the role of the Mn centre as the only active site involved in both elementary steps, namely hydride borrowing and C-O bond formation. During this C-O bond formation step, diastereoisomers (R-N,R) and (R-N,S) [or their enantiomeric pairs (S-N,S) and (S-N,R)] can be generated, with calculations showing a preference towards the (R-N,R) pathway.en_US
dc.languageengen_US
dc.relation.ispartofTheoretical Chemistry Accountsen_US
dc.sourceTheoretical Chemistry Accounts[ISSN 1432-881X],v. 138 (5)en_US
dc.subject3303 ingeniería y tecnología químicasen_US
dc.subject.otherSolvation Free-Energiesen_US
dc.subject.otherAlkynesen_US
dc.subject.otherHydrogenationen_US
dc.subject.otherSemihydrogenationen_US
dc.subject.otherAldehydesen_US
dc.subject.otherAlcoholsen_US
dc.subject.otherAminesen_US
dc.subject.otherIonsen_US
dc.titleUnravelling the reaction mechanism for the Claisen-Tishchenko condensation catalysed by Mn(I)-PNN complexes: a DFT studyen_US
dc.typeinfo:eu-repo/semantics/Articleen_US
dc.typeArticleen_US
dc.identifier.doi10.1007/s00214-019-2449-7en_US
dc.identifier.scopus85065149209-
dc.identifier.isi000466976000001-
dc.contributor.authorscopusid55142490200-
dc.contributor.authorscopusid57204926818-
dc.identifier.eissn1432-2234-
dc.identifier.issue5-
dc.relation.volume138en_US
dc.investigacionCienciasen_US
dc.type2Artículoen_US
dc.contributor.daisngid1089199-
dc.contributor.daisngid24922-
dc.utils.revisionen_US
dc.contributor.wosstandardWOS:Azofra, LM-
dc.contributor.wosstandardWOS:Cavallo, L-
dc.date.coverdateMayo 2019en_US
dc.identifier.ulpgcen_US
dc.description.sjr0,4
dc.description.jcr1,498
dc.description.sjrqQ3
dc.description.jcrqQ4
dc.description.scieSCIE
item.grantfulltextopen-
item.fulltextCon texto completo-
crisitem.author.deptGIR Fotocatálisis y espectroscopía para aplicaciones medioambientales. Unidad asociada al CSIC a través del Instituto de Ciencias de Materiales de Sevilla-
crisitem.author.deptIU de Estudios Ambientales y Recursos Naturales-
crisitem.author.orcid0000-0003-4974-1670-
crisitem.author.parentorgIU de Estudios Ambientales y Recursos Naturales-
crisitem.author.fullNameAzofra Mesa, Luis Miguel-
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