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dc.contributor.authorPeñas de Frutos, Marconi Nicolás 
dc.contributor.authorBartolomé Albistegui, María del Camino 
dc.contributor.authorEspinet Rubio, Pablo 
dc.date.accessioned2018-11-14T08:34:33Z
dc.date.issued2018
dc.identifier.citationOrganometallics, 2018, 37 (20), pp 3533–3542es
dc.identifier.issn0276-7333es
dc.identifier.urihttp://uvadoc.uva.es/handle/10324/32632
dc.descriptionProducción Científicaes
dc.description.abstractThe pentacoordinated [RhCp*Rf2] (Rf = C6F3Cl2-3,5) and the octahedral (μ-Cl)2[RhCp*Rf]2, obtained by stoichiometric rearrangement with (μ-Cl)2[RhCp*Cl]2, are general precursors of [RhCp*RfXL] (X = Rf, Cl; L = ligand) complexes, which were studied by NMR (L dissociation and fluxional processes) and X-ray diffraction (structural effects affecting the Rh–Cp* distances) techniques. The Rh–Cp*centroid distances decrease markedly for identical L in the order [RhCp*Rf2L] > [RhCp*RfClL] > [RhCp*Cl2L] and are further influenced regularly within each family by the trans influence of L (longer distances for higher trans influence of L). The structural effects observed reveal a remarkable capability of Cp* to act as an electron-density buffer, which attenuates the Rh electron density variations induced by the substituents in front of Cp* by releasing toward Rh or polarizing toward Cp*, on demand, the electron density of the Rh–Cp* bonds. This buffer effect explains the easy L dissociation from [RhCp*Rf2L] and the accessibility to formally 16e pentacoordinated [RhCp*Rf2].es
dc.format.mimetypeapplication/pdfes
dc.language.isoenges
dc.publisherAmerican Chemical Societyes
dc.rights.accessRightsinfo:eu-repo/semantics/openAccesses
dc.subject.classificationQuímica organometálicaes
dc.subject.classificationOrganometallic chemistryes
dc.titleCoordinatively Unsaturated [RhCp*Rf2] (Cp* = C5Me5; Rf = C6F3Cl2-3,5), General Precursor to Cp*-Diaryl and Cp*-Halo-Aryl RhIII Complexes. Observing and Testing the Effect of Cp* as Electronic Bufferes
dc.typeinfo:eu-repo/semantics/articlees
dc.rights.holder© American Chemical Societyes
dc.identifier.doihttps://doi.org/10.1021/acs.organomet.8b00227es
dc.relation.publisherversionhttps://pubs.acs.org/doi/10.1021/acs.organomet.8b00227es
dc.peerreviewedSIes
dc.description.embargo2019-09-09es
dc.description.lift2019-09-09
dc.description.projectMinisterio de Economía, Industria y Competitividad (Projects CTQ2016-80913-P, CTQ2014-52796-P, and CTQ2017-89217-P)es
dc.description.projectJunta de Castilla y León (programa de apoyo a proyectos de investigación - Ref. VA051P17)es


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