dc.contributor.author | Carbó, Jorge J. | |
dc.contributor.author | Gómez Pantoja, María | |
dc.contributor.author | Martín Alonso, Avelino | |
dc.contributor.author | Mena Montoro, Miguel | |
dc.contributor.author | Ricart, Josep M. | |
dc.contributor.author | Salom Catalá, Antoni | |
dc.contributor.author | Santamaría Angulo, Cristina | |
dc.date.accessioned | 2019-09-06T06:15:40Z | |
dc.date.issued | 2019-08-26 | |
dc.identifier.bibliographicCitation | Inorganic Chemistry, 2019, v. 58, n. 18, p. 12157-12166 | en |
dc.identifier.issn | 0020-1669 | |
dc.identifier.uri | http://hdl.handle.net/10017/38966 | en |
dc.description.abstract | Treatment of the dinuclear compound [{Ti(η5-C5Me5)Cl2}2(μ-O)] with allylmagnesium chloride provides the formation of the allyltitanium(III) derivative [{Ti(η5-C5Me5)(μ-C3H5)}2(μ-O)] (1), structurally identified by single-crystal X-ray analysis. Density functional theory (DFT) calculations confirm that the electronic structure of 1 is a singlet state, and the molecular orbital analysis, along with the short Ti −Ti distance, reveal the presence of a metal −metal single bond between the two Ti(III) centers. Complex 1 reacts rapidly with organic azides, RN3 (R = Ph, SiMe3), to yield the allyl μ-imido derivatives [{Ti(η5-C5Me5)(CH2CH=CH2)}2(μ-NR)(μ-O)] [R = Ph(2), SiMe3(3)] along with molecular nitrogen release. Reaction of 2 and 3 with H2 leads to the μ-imido propyl species [{Ti(η5-C5Me5)(CH2CH2CH3)}2(μ-NR)(μ-O)] [R = Ph(4), SiMe3(5)]. Theoretical calculations were used to gain insight into the hydrogenation mechanism of complex 3 and rationalize the lower reactivity of 2. Initially, the μ-imido bridging group in these complexes activates the H2 molecule via addition to the Ti −N bonds. Subsequently, the titanium hydride intermediates induce a change in hapticity of the allyl ligands, and the nucleophilic attack of the hydride to the allyl groups leads to metallacyclopropane intermediates. Finally, the proton transfer from the amido group to the metallacyclopropane moieties affords the propyl complexes 4 and 5. | en |
dc.description.sponsorship | Ministerio de Ciencia, Innovación y Universidades
Universidad de Alcalá
Generalitat de Catalunya | es_ES |
dc.format.mimetype | application/pdf | en |
dc.language.iso | eng | en |
dc.rights | Attribution-NonCommercial-ShareAlike 4.0 International (CC BY-NC-SA 4.0) | en |
dc.rights | © 2019 American Chemical Society | en |
dc.rights.uri | http://creativecommons.org/licenses/by-nc-sa/4.0/ | en |
dc.title | A Bridging bis-Allyl Titanium Complex: Mechanistic Insights into the Electronic Structure and Reactivity | 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 | 2019-09-06T06:13:52Z | |
dc.type.version | info:eu-repo/semantics/publishedVersion | en |
dc.identifier.doi | 10.1021/acs.inorgchem.9b01505 | en |
dc.relation.projectID | PGC2018-094007-B-I00
CCG2018/EXP-026
2014SGR199 | es_ES |
dc.date.embargoEndDate | 2020-08-27 | |
dc.rights.accessRights | info:eu-repo/semantics/openAccess | en |
dc.identifier.uxxi | AR/0000031435 | en |
dc.identifier.publicationtitle | Inorganic Chemistry | en |
dc.identifier.publicationvolume | 58 | |
dc.identifier.publicationlastpage | 12166 | |
dc.identifier.publicationissue | 18 | |
dc.identifier.publicationfirstpage | 12157 | |