dc.creator | Sandoval, John J. | es |
dc.creator | Palma, Pilar | es |
dc.creator | Álvarez González, Eleuterio | es |
dc.creator | Cámpora Pérez, Juan | es |
dc.creator | Rodríguez Delgado, Antonio | es |
dc.date.accessioned | 2018-07-13T08:28:30Z | |
dc.date.available | 2018-07-13T08:28:30Z | |
dc.date.issued | 2016 | |
dc.identifier.citation | Sandoval, J.J., Palma, P., Álvarez González, E., Cámpora, J. y Rodríguez Delgado, A. (2016). Mechanism of Alkyl Migration in Diorganomagnesium 2,6-Bis(imino)pyridine Complexes: Formation of Grignard-Type Complexes with Square-Planar Mg(II) Centers. Organometallics, 35 (18), 3197-3204. | |
dc.identifier.issn | 0276-7333 (impreso) | es |
dc.identifier.issn | 1520-6041 (electrónico) | es |
dc.identifier.uri | https://hdl.handle.net/11441/77232 | |
dc.description.abstract | Dialkylmagnesium compounds [MgR2L2] (R = n-Bu, L = none or R = Bn, L = THF) react with 2,6-bis(imino)pyridines (BIP) to afford different types of Mg(II) alkyl complexes, depending on the nature of R. For R = n-Bu, thermally stable products resulting from selective alkyl transfer to the pyridine nitrogen (N1) atom are obtained. However, NMR studies showed that the reaction of [Mg(Bn)2THF2] with iPrBIP at −65 °C leads to a thermally unstable product arising from benzyl migration to position C2 in the pyridine ring. Above +5 °C, this compound rearranges, cleanly yielding a mixture of two isomeric complexes, in which the benzyl group has migrated to positions C3 or C4 of the central ring, respectively. Similar isomeric mixtures were obtained when [Mg(Bn)2THF2] was reacted with iPrBIP or MesBIP at room temperature. Such mixtures are thermally stable below 80 °C, but at this temperature, the 3-benzyl isomer converts into the thermodynamically favored 4-benzyl product, albeit not quantitatively. An alternate route was devised for the selective syntheses of the latter type of compounds. The X-ray diffraction structure of one of them provided an unusual example of a square-planar alkylmagnesium(II) center. | es |
dc.description.sponsorship | Ministerio de Economía e Innovación CTQ2015-68978- P | es |
dc.format | application/pdf | es |
dc.language.iso | eng | es |
dc.publisher | American Chemical Society | es |
dc.relation.ispartof | Organometallics, 35 (18), 3197-3204. | |
dc.rights | Attribution-NonCommercial-NoDerivatives 4.0 Internacional | * |
dc.rights.uri | http://creativecommons.org/licenses/by-nc-nd/4.0/ | * |
dc.title | Mechanism of Alkyl Migration in Diorganomagnesium 2,6-Bis(imino)pyridine Complexes: Formation of Grignard-Type Complexes with Square-Planar Mg(II) Centers | es |
dc.type | info:eu-repo/semantics/article | es |
dcterms.identifier | https://ror.org/03yxnpp24 | |
dc.type.version | info:eu-repo/semantics/acceptedVersion | es |
dc.rights.accessRights | info:eu-repo/semantics/openAccess | es |
dc.relation.publisherversion | http://dx.doi.org/10.1021/acs.organomet.6b00528 | es |
dc.identifier.doi | 10.1021/acs.organomet.6b00528 | es |
idus.format.extent | 9 | es |
dc.journaltitle | Organometallics | es |
dc.publication.volumen | 35 | es |
dc.publication.issue | 18 | es |
dc.publication.initialPage | 3197 | es |
dc.publication.endPage | 3204 | es |
dc.contributor.funder | Ministerio de Economía y Competitividad (MINECO). España | |