dc.contributor.author | Carbó, Jorge J. | |
dc.contributor.author | Martínez Espada, Noelia | |
dc.contributor.author | Mena Montoro, Miguel | |
dc.contributor.author | González Mosquera, Marta Elena | |
dc.contributor.author | Poblet Rius, Josep María | |
dc.contributor.author | Yélamos Sánchez, Carlos | |
dc.date.accessioned | 2019-09-09T10:58:42Z | |
dc.date.available | 2019-09-09T10:58:42Z | |
dc.date.issued | 2009-11-02 | |
dc.identifier.bibliographicCitation | Chemistry - A European Journal, 2009, v. 15, n. 43, p. 11619-11631 | en |
dc.identifier.issn | 0947-6539 | |
dc.identifier.uri | http://hdl.handle.net/10017/39008 | en |
dc.description.abstract | The Lewis base behavior of mu(3)-nitrido ligands of the polynuclear titanium complexes [{Ti(eta(5)-C(5)Me(5))(mu-NH)}(3)(mu(3)-N)] (1) and [{Ti(eta(5)-C(5)Me(5))}(4)-(mu(3)-N)(4)] (2) to MX Lewis acids has been observed for the first time. Complex 1 entraps one equivalent of copper(I) halide or copper(I) trifluorornethanesulfonate through the basal NH imido groups to give cube-type adducts [XCu{(mu(3)-NH)(3)Ti(3)(eta(5)-C(5)Me(5))(3)(mu(3)-N)}] (X=Cl (3), Br (4), I (5), OSO(2)CF(3) (6)). However, the treatment of 1 with an excess (>= 2 equiv) of copper reagents afforded complexes [XCu{(mu(3)-NH)(3)Ti(3)(eta(5)-C(5)Me(5))(3)(mu(4)-N)(CuX)}] (X=Cl (7), Br (8), I (9) OSO(2)CF(3) (10)) by incorporation of an additional CuX fragment Lit the mu(3)-N nitrido apical group. Similarly, the tetranuclear cube-type nitrido derivative 2 is capable of incorporating one, two, or up to three CuX units at the mu(3)-N ligands to give complexes [{Ti(eta(5)-C(5)Me(5))}(4)(mu(3)-N)(4-n)-{(mu(4)-N)CuX}(n)] (X=Br (11), n=1; X=Cl (12) n=2; X=OSO(2)CF(3) (13), n=3). Compound 2 also reacts with silver(I) trifluoromethanesulfortate (>= 1 equiv) to give the adduct [{Ti(eta(5)-C(5)Me(5))}(4)(mu(3)-N)(3){(mu(4)-N)AgOSO(2)CF(3)}] (14). X-ray crystal structure determinations have been performed for complexes 8-13. Density functional theory calculations have been carried out to understand the nature and strength of the interactions of [{Ti(eta(5)-C(5)H(5))(mu-NH)}(3)(mu(3)-N)] (1') and [{Ti(eta(5)-C(5)H(5))}(4)-(mu(3)-N)(4)] (2') model complexes with copper and silver MX fragments. Although coordination through the three basal NH imido groups is thermodynamically preferred in the case of V, in both complexes the mu(3)-nitrido groups act as two-electron donor Lewis bases to the appropriate Lewis acids. | en |
dc.description.sponsorship | MINISTERIO DE EDUCACIÓN Y CIENCIA, COMUNIDAD DE MADRID, UNIVERSIDAD DE ALCALÁ, GENERALITAT DE CATALUNYA | 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 | © Wiley-VCH Verlag GmbH&Co. KGaA, 2009 | en |
dc.rights.uri | http://creativecommons.org/licenses/by-nc-nd/4.0/ | en |
dc.subject | cage compounds | en |
dc.subject | cubanes | en |
dc.subject | density functional calculations | en |
dc.subject | nitrides | en |
dc.subject | titanium | en |
dc.title | Lewis Base Behavior of Bridging Nitrido Ligands of Titanium Polynuclear Complexes | 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 | 2019-09-09T10:57:48Z | |
dc.type.version | info:eu-repo/semantics/publishedVersion | en |
dc.identifier.doi | 10.1002/chem.200901598 | en |
dc.relation.projectID | CTQ2008-00061/BQU, CTQ2008-06549-C02-01/BQU,CCG06-UAH/PPQ-0665, 2005SGR-00104, FACTORÍA DE CRISTALIZACIÓN (CONSOLIDER-INGENIO 2010 CSD2006-00015). | es_ES |
dc.rights.accessRights | info:eu-repo/semantics/openAccess | en |
dc.identifier.uxxi | AR/0000010509 | en |
dc.identifier.publicationtitle | Chemistry - A European Journal | en |
dc.identifier.publicationvolume | 15 | |
dc.identifier.publicationlastpage | 11631 | |
dc.identifier.publicationissue | 43 | |
dc.identifier.publicationfirstpage | 11619 | |