dc.contributor.author | Ciruelos Ortega, Santiago | |
dc.contributor.author | Sebastián Navas, Alfredo | |
dc.contributor.author | Cuenca Agreda, José Tomás | |
dc.contributor.author | Gómez Sal, Pilar | |
dc.contributor.author | Manzanero Castillo, Antonio | |
dc.contributor.author | Royo Gracia, Pascual | |
dc.date.accessioned | 2009-10-06T10:19:58Z | |
dc.date.available | 2009-10-06T10:19:58Z | |
dc.date.issued | 2000 | |
dc.identifier.bibliographicCitation | Journal of Organometallic Chemistry, 2000, v. 604, p. 103-115 | en |
dc.identifier.issn | 0022-328X | |
dc.identifier.uri | http://hdl.handle.net/10017/4208 | |
dc.description.abstract | Reaction of the disilylated cyclopentadiene C5H4(SiClMe2)(SiMe3) with HfCl4, in heptane, gave the monocyclopentadienyl complex Hf(η5-C5H4SiClMe2)Cl3 (1c). Addition of two equivalents of C5H5(SiClMe2) to a solution of MCl4, in toluene under reflux and in the presence of two equivalents of NEt3, afforded the dichloro derivatives M(η5-C5H4SiClMe2)2Cl2 [M=Ti (2a), Hf (2c)]. Compounds 2a and 2c react with a stoichiometric amount of water with selective hydrolysis of the SiCl bonds to give the tetramethyldisiloxane-bridged diciclopentadienyl complexes M{(η5-C5H4)SiMe2OSiMe2(η5-C5H4)}Cl2 [M=Ti (3a), Hf (3c)]. The reaction of the trichloro metal compounds M(η5-C5H4SiClMe2)Cl3 with Tl(1,3-tBu2C5H3), K(C5Me5) or Tl(C5H5) afforded the dichloro mixed dicyclopentadienyl MCp′(η5-C5H4SiClMe2)Cl2 derivatives [Cp′=1,3-tBu2C5H3, M=Ti (4a), Zr (4b), Hf (4c); Cp′=C5Me5, M=Zr (5b), Hf (5c); Cp′=C5H5, M=Hf (6c)]. The SiCl bond of the mixed dicyclopentadienyl complexes M(η5-1,3-tBu2C5H3)(η5-C5H4SiClMe2)Cl2, [M=Ti (4a), Zr (4b), Hf (4c)] reacts selectively with one equivalent of LiNHtBu in toluene at 50–60°C to give the amidosilyl(cyclopentadienyl) compounds M(η5-1,3-tBu2C5H3)(η5-C5H4SiMe2NHtBu)Cl2, [M=Ti (7a), Zr (7b), Hf (7c)]. The same reaction with two equivalents of the lithium amide gives the ansa-cyclopentadienylsilyl-amido compounds M(η5-1,3-tBu2C5H3)(η5-C5H4SiMe2-η-NtBu)Cl [M=Ti (8a), Zr (8b), Hf (8c)]. The X-ray molecular structure of Hf{(η5-C5H4)SiMe2OSiMe2(η5-C5H4)}Cl2 (3c) and Zr(η5-1,3-tBu2C5H3)(η5-C5H4SiMe2-η-NtBu)Cl (8b) have been determined by diffraction methods. | en |
dc.description.sponsorship | Financial support for this research by DGICYT (Project PB97-0776) is gratefully acknowledged. | en |
dc.format.mimetype | application/pdf | en |
dc.language.iso | eng | en |
dc.publisher | Elsevier | en |
dc.rights | (c) Elsevier, 2000 | en |
dc.subject | Titanium | en |
dc.subject | Zirconium | en |
dc.subject | Hafnium | en |
dc.subject | Chlorodimethylsilyl-cyclopentadienyl | en |
dc.subject | Mixed dicyclopentadienyl | en |
dc.subject | Amido cyclopentadienyl | en |
dc.title | Synthetic and reactivity studies of mono- and dicyclopentadienyl titanium, zirconium and hafnium complexes with the chlorodimethylsilyl-cyclopentadienyl ligand. X-ray molecular structure of Hf{(η5-C5H4)SiMe2OSiMe2(η5-C5H4)}Cl2 and Zr(η5-1,3-tBu2C5H3)(η5-C5H4SiMe2-η-NtBu)Cl | 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/10.1016/S0022-328X(00)00213-8 | |
dc.type.version | info:eu-repo/semantics/publishedVersion | en |
dc.identifier.doi | 10.1016/S0022-328X(00)00213-8 | |
dc.relation.projectID | PB97-0776 (Ministerio de Ciencia y Tecnología) | |
dc.rights.accessRights | info:eu-repo/semantics/openAccess | en |