dc.contributor.author | Caballo González, Jorge | |
dc.contributor.author | González Moreiras, Mariano | |
dc.contributor.author | Mena Montoro, Miguel | |
dc.contributor.author | Pérez Redondo, Adrián | |
dc.contributor.author | Yélamos Sánchez, Carlos | |
dc.date.accessioned | 2019-07-03T07:38:58Z | |
dc.date.available | 2019-07-03T07:38:58Z | |
dc.date.issued | 2013-10-07 | |
dc.identifier.bibliographicCitation | Inorganic Chemistry, 2013, v. 52, n. 19, p. 11519-11529 | en |
dc.identifier.issn | 0020-1669 | |
dc.identifier.uri | http://hdl.handle.net/10017/38427 | en |
dc.description.abstract | Several trinuclear titanium complexes bearingamido mu-NHR, imido mu-NR, and nitrido mu(n)-N ligands have been prepared by reaction of [{Ti(eta(5)-C5Me5)(mu-NH)}(3)(mu(3)-N)] (1) with 1 equiv of electrophilic reagents ROTf (R = H, Me, SiMe3; OTf = OSO2CF3). Treatment of 1 with triflic acid or methyl triflate in toluene at room temperature affords the precipitation of compounds [Ti-3(eta(5)-C5Me5)(3)(mu(3)-N)(mu-NH)(2)(mu-NH2)(OTf)] (2) or [Ti-3(eta(5)-C5Me5)(3)(mu(3)-N)(mu-NH)(mu-NH2)(mu-NMe)(OTf)](3). Complexes 2 and 3 exhibit a fluxional behavior in solution consisting of proton exchange between mu-NH2 and mu-NH groups, assisted by the triflato ligand, as could be inferred from a dynamic NMR spectroscopy study. Monitoring by NMR spectroscopy the reaction course. of 1 with MeOTf allows the characterization of the methylamido intermediate [Ti-3(eta(5)-C5Me5)(3)(mu(3)-N)(mu-NH)(2)(mu-NHMe)(OTf)] (4), which readily rearranges to give 3 by a proton migration from the NHMe amido group to the NH imido ligands. The treatment of 1 with 1 equiv ofMe3SiOTf produces the stable ionic complex [Ti-3(eta(5)-C5Me5)(3)(mu(3)-N)(mu-NH)(2)(mu-NHSiMe3)][OTf] (5) with a disposition of the nitrogen ligands similar to that of 4. Complex 5 reacts with 1 equiv of [K{N(SiMe3)(2)}] at room temperature to give [Ti-3(eta(5)-C5Me5)(3)(mu(3)-N)(mu-N)(mu-NH)(mu-NHSiMe3)] (6), which at 85 degrees C rearranges to the trimethylsilylimido derivative [Ti-3(eta(5)-C5Me5)(3)(mu(3)-N)(mu-NH)(2)(mu-NHSiMe3)] (7). Treatment of 7 with [K{N(SiMe3)(2)}] affords the potassium derivative [K{(mu(3)-N)(mu(3)-NH)(mu(3)-NiSMe3)Ti-3(eta(C5Me5)-C-5)(3)(mu(3)-N)}] (8), which upon addition of 18-crown-6 leads to the ion pair [K(18-crown-6)] [Ti-3(eta(5)-C5Me5)(3)(mu(3)-N)(mu-NH)(mu-NHSiMe3)] (9). The X-ray crystal structures of2, 5, 6, and 8 have been determined. | en |
dc.description.sponsorship | Ministerio de Ciencia e Innovación de España, Comunidad de Madrid, Universidad de Alcalá, Ministerio de Educación y Ciencia de España | es_ES |
dc.format.mimetype | application/pdf | en |
dc.language.iso | eng | en |
dc.rights | Attribution-NonCommercial-NoDerivatives 4.0 International (CC BY-NC-ND 4.0) | en |
dc.rights | © American Chemical Society, 2013 | en |
dc.rights.uri | http://creativecommons.org/licenses/by-nc-nd/4.0/ | en |
dc.title | Reactivity with Electrophiles of Imido Groups Supported on Trinuclear Titanium Systems | en |
dc.type | info:eu-repo/semantics/article | en |
dc.subject.eciencia | Química | es_ES |
dc.subject.eciencia | Chemistry | en |
dc.contributor.affiliation | Universidad de Alcalá. Departamento de Química Orgánica y Química Inorgánica | |
dc.date.updated | 2019-07-03T07:32:33Z | |
dc.type.version | info:eu-repo/semantics/publishedVersion | en |
dc.identifier.doi | 10.1021/ic4018294 | |
dc.relation.projectID | CTQ2008-00061/BQU, CCG10-UAH/PPQ-5935, "Factoría de Cristalización" CONSOLIDER-INGENIO 2010 CSD2006-00015 | es_ES |
dc.rights.accessRights | info:eu-repo/semantics/openAccess | en |
dc.identifier.uxxi | AR/0000018539 | en |
dc.identifier.publicationtitle | Inorganic Chemistry | en |
dc.identifier.publicationvolume | 52 | |
dc.identifier.publicationlastpage | 11529 | |
dc.identifier.publicationissue | 19 | |
dc.identifier.publicationfirstpage | 11519 | |