dc.contributor.author | Postigo Galindo, Lorena | |
dc.contributor.author | Sánchez-Nieves Fernández, Javier | |
dc.contributor.author | Royo Gracia, Pascual | |
dc.contributor.author | González Mosquera, Marta Elena | |
dc.date.accessioned | 2009-10-01T08:30:27Z | |
dc.date.available | 2009-10-01T08:30:27Z | |
dc.date.issued | 2009 | |
dc.identifier.bibliographicCitation | Dalton Transactions, 2009, v.19, p.3756-3765 | en |
dc.identifier.issn | 1477-9226 | |
dc.identifier.uri | http://hdl.handle.net/10017/4168 | |
dc.description.abstract | The dinuclear dialkoxo-bridged complexes [(TiCl)2(μ-O2L)(μ-{(η5-C5Me4SiMeO)2(μ-O)})] (O2L = 1,2-O2C2H41a, 1,2-O2C6H41b, 1,2-(OCH2)2C6H41c, O2SiPh21d) were obtained by reaction of [(TiCl2)2(μ-{(η5-C5Me4SiMeO)2(μ-O)})] (A) with the corresponding dilithium salt (1a) or diol (1b, 1c, 1d). Alkylation of 1a and 1b with ClRMg afforded [(TiR)2(μ-O2L)(μ-{(η5-C5Me4SiMeO)2(μ-O)})] (O2L = 1,2-O2C2H4, R = Me 2a, Bz 3a; O2L = 1,2-O2C6H4, R = Me 2b, Bz 3b). Addition of four equiv. of LiOiPr to A afforded [{Ti(OiPr)2}2(μ-{(η5-C5Me4SiMeO)2(μ-O)})] (4). Reaction of 1a with Al(C6F5)3 produced the elimination of the dialkoxo ligand to give [{TiCl(C6F5)}2(μ-{(η5-C5Me4SiMeO)2(μ-O)})] (5), whereas the same reaction of 1b with Al(C6F5)3 produced the oxo-alane adduct [(TiCl)2(μ-O2L)(μ-{(η5-C5Me4SiMeO)2(μ-O·Al{C6F5}3)})] (O2L = 1,2-O2C6H46) which was further transformed to give a mixture of 5 and [(TiCl){Ti(C6F5)}(μ-O2L)(μ-{(η5-C5Me4SiMeO)2(μ-O)})] (O2L = 1,2-O2C6H47). One benzyl group of complexes 3 was abstracted with E(C6F5)3 (E = B, Al) to give the monoionic compounds [Ti(TiBz)(μ-O2L)(μ-{(η5-C5Me4SiMeO)2(μ-O)})][BzE(C6F5)3] (O2L = 1,2-O2C2H4, E = B 8B, Al 8Al; O2L = 1,2-O2C6H4, E = B 9B), although 8Al was unstable in CD2Cl2 evolving to a mixture of compounds where [(TiBz)2(μ-Cl)(μ-{(η5-C5Me4SiMeO)2(μ-O)})][BzAl(C6F5)3] (10) was identified, and compound 9B was also unstable at ambient temperature. Polymerization of ε-caprolactone was only achieved with the tetraalkoxo compound 4. All of these complexes were characterized by NMR spectroscopy and 1a, 1b and 7 by X-ray diffraction studies. | en |
dc.format.mimetype | application/pdf | en |
dc.language.iso | eng | en |
dc.publisher | Royal Society of Chemistry | en |
dc.rights | © Royal Society of Chemistry, 2015 | en |
dc.subject | Cyclopentadienylsiloxo titanium | en |
dc.title | Dinuclear dialkoxo-bridged cyclopentadienylsiloxo titanium complexes | en |
dc.type | info:eu-repo/semantics/article | en |
dc.subject.eciencia | Ciencia | es_ES |
dc.subject.eciencia | Química inorgánica | es_ES |
dc.subject.eciencia | Science | en |
dc.subject.eciencia | Chemistry, inorganic | en |
dc.contributor.affiliation | Universidad de Alcalá. Departamento de Química Inorgánica | |
dc.relation.publisherversion | http://dx.doi.org/10.1039/B820092K | |
dc.type.version | info:eu-repo/semantics/publishedVersion | en |
dc.identifier.doi | 10.1039/B820092K | |
dc.relation.projectID | MAT2007–60997 (Ministerio de Educación y Ciencia) | |
dc.relation.projectID | S-0505/PPQ-0328/COMAL (Comunidad de Madrid | |
dc.rights.accessRights | info:eu-repo/semantics/openAccess | en |