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dc.contributor.authorGómez-Pantoja Güemes, María 
dc.contributor.authorGonzález Pérez, Juan Ignacio 
dc.contributor.authorMartín Alonso, Avelino 
dc.contributor.authorMena Montoro, Miguel 
dc.contributor.authorSantamaría Angulo, Cristina 
dc.contributor.authorTemprado Morena, Manuel 
dc.date.accessioned2019-09-04T10:31:03Z
dc.date.available2019-09-04T10:31:03Z
dc.date.issued2018-06-22
dc.identifier.bibliographicCitationOrganometallics, 2018, v. 37, n. 13, p. 2046-2053en
dc.identifier.issn0276-7333
dc.identifier.urihttp://hdl.handle.net/10017/38900en
dc.description.abstractThe reactivity of the "tuck-over" species [Ti2(η5-C5Me5)(CH2Ph)3(μ-η5-C5Me4CH2-κC)(μ-O)] (1) and [Ti2(η5-C5Me5)(CH2CMe3)(μ-η5-C5Me4CH2-κC)(μ-CH2CMe2CH2)(μ-O)] (2) toward isocyanides has been examined both synthetically and theoretically. Treatment of 1with the isocyanides RNC, R = Me3SiCH2, 2,6-Me2C6H3, tBu,iPr, leads to a series of η2-iminoacyl species (3−6) where the molecule of isocyanide inserts into one of the terminal metal−alkyl bonds. The analogous reaction of the "tuck-over" metallacycle species 2 with 2,6-Me2C6H3NC andtBuNC results inthe initial insertion of one isocyanide into the terminal Ti−alkyl bondto form the iminoacyl complexes 7 and 8, followed by a secondinsertion into the metallacycle moiety to generate 9, in the case of tertbutylisocyanide. DFT calculations support the selective reactivity observed experimentally with a kinetic and thermodynamicpreference for RNC insertion on the terminal alkyl groups bound to both metallic centers over the alternative insertion on the "tuck-over"ligand.en
dc.description.sponsorshipMinisterio de Economía y Competitividad Universidad de Alcaláes_ES
dc.format.mimetypeapplication/pdfen
dc.language.isoengen
dc.rightsAttribution-NonCommercial-NoDerivatives 4.0 International (CC BY-NC-ND 4.0)en
dc.rights© 2018 American Chemical Societyen
dc.rights.urihttp://creativecommons.org/licenses/by-nc-nd/4.0/en
dc.titleReactivity of Tuck-over Titanium Oxo Complexes with Isocyanidesen
dc.typeinfo:eu-repo/semantics/articleen
dc.subject.ecienciaQuímicaes_ES
dc.subject.ecienciaChemistryen
dc.contributor.affiliationUniversidad de Alcalá. Departamento de Química Analítica, Química Física e Ingeniería Química
dc.contributor.affiliationUniversidad de Alcalá. Departamento de Química Orgánica y Química Inorgánica
dc.date.updated2019-09-04T10:29:55Z
dc.type.versioninfo:eu-repo/semantics/publishedVersionen
dc.identifier.doi10.1021/acs.organomet.8b00212en
dc.relation.projectIDCTQ2016-80600-P CCG2016/EXP-009es_ES
dc.relation.projectIDinfo:eu-repo/grantAgreement/MINECO//CTQ2013-44625-R/ES/ACTIVACION Y FUNCIONALIZACION DE DINITROGENO EN COMPLEJOS POLIMETALICOS COMO ALTERNATIVA AL PROCESO HABER-BOSCH EN LA PRODUCCION DE AMONIACO/es_ES
dc.rights.accessRightsinfo:eu-repo/semantics/openAccessen
dc.identifier.uxxiAR/0000028632en
dc.identifier.publicationtitleOrganometallicsen
dc.identifier.publicationvolume37
dc.identifier.publicationlastpage2053
dc.identifier.publicationissue13
dc.identifier.publicationfirstpage2046


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