dc.creator | Martínez Prieto, Luis Miguel | es |
dc.creator | Ávila, Elena | es |
dc.creator | Palma Ramírez, María del Pilar | es |
dc.creator | Álvarez González, Eleuterio | es |
dc.creator | Cámpora Pérez, Juan | es |
dc.date.accessioned | 2017-11-02T17:25:12Z | |
dc.date.available | 2017-11-02T17:25:12Z | |
dc.date.issued | 2015 | |
dc.identifier.citation | Martínez Prieto, L.M., Ávila, E., Palma, P., Álvarez González, E. y Cámpora, J. (2015). β-Hydrogen Elimination Reactions of Nickel and Palladium Methoxides Stabilised by PCP Pincer Ligands. Chemistry - a European Journal, 21 (27), 9833-9849. | |
dc.identifier.issn | 0947-6539 (impreso) | es |
dc.identifier.issn | 1521-3765 (electrónico) | es |
dc.identifier.uri | http://hdl.handle.net/11441/65616 | |
dc.description.abstract | Nickel and palladium methoxides [((iPr)PCP)M-OMe], which contain the (iPr)PCP pincer ligand, decompose upon heating to give products of different kinds. The palladium derivative cleanly gives the dimeric Pd(0) complex [Pd(μ-(iPr)PCHP)]2 ((iPr)PCHP = 2,6-bis(diisopropylphosphinomethyl)phenyl) and formaldehyde. In contrast, decomposition of [((iPr)PCP)Ni-OMe] affords polynuclear carbonyl phosphine complexes. Both decomposition processes are initiated by β-hydrogen elimination (BHE), but the resulting [((iPr)PCP)M-H] hydrides undergo divergent reaction sequences that ultimately lead to the irreversible breakdown of the pincer units. Whereas the Pd hydride spontaneously experiences reductive C-H coupling, the decay of its Ni analogue is brought about by its reaction with formaldehyde released in the BHE step. Kinetic measurements showed that the BHE reaction is reversible and less favourable for Ni than for Pd for both kinetic and thermodynamic reasons. DFT calculations confirmed the main conclusions of the kinetic studies and provided further insight into the mechanisms of the decomposition reactions. | es |
dc.description.sponsorship | Gobierno de España CTQ2012-30962 | es |
dc.description.sponsorship | Junta de Andalucía FQM6276 | es |
dc.format | application/pdf | es |
dc.language.iso | eng | es |
dc.publisher | John Wiley & Sons | es |
dc.relation.ispartof | Chemistry - a European Journal, 21 (27), 9833-9849. | |
dc.rights | Attribution-NonCommercial-NoDerivatives 4.0 Internacional | * |
dc.rights.uri | http://creativecommons.org/licenses/by-nc-nd/4.0/ | * |
dc.subject | Alcohol oxidation | es |
dc.subject | Alkoxides | es |
dc.subject | Dehydrogenation | es |
dc.subject | Pincer ligands | es |
dc.subject | Reaction mechanisms | es |
dc.title | β-Hydrogen Elimination Reactions of Nickel and Palladium Methoxides Stabilised by PCP Pincer Ligands | 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.projectID | CTQ2012-30962 | es |
dc.relation.projectID | FQM6276 | es |
dc.relation.publisherversion | http://dx.doi.org/10.1002/chem.201500652 | es |
dc.identifier.doi | 10.1002/chem.201500652 | es |
idus.format.extent | 18 p. | es |
dc.journaltitle | Chemistry - a European Journal | es |
dc.publication.volumen | 21 | es |
dc.publication.issue | 27 | es |
dc.publication.initialPage | 9833 | es |
dc.publication.endPage | 9849 | es |
dc.contributor.funder | Gobierno de España | |
dc.contributor.funder | Junta de Andalucía | |