Diastereoselective insertion of isocyanide into the alkyl metal bond of methylbenz[e]indenyl ansa-zirconocene complexes
Alkylation of ansa-zirconocene [Zr{(η5-C5H5)SiMe2(MBI)}Cl2] (MBI = η5-2-Me−C13H7) with MgRCl gave the dimethyl complex [Zr{(η5-C5H5)SiMe2(MBI)}Me2], but unresolvable mixtures containing mono-alkylated compounds were obtained when bulkier alkyls were used. However pure dialkyl complexes [Zr{(η5-C5H5)...
| Autores: | , , , |
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| Tipo de recurso: | artículo |
| Fecha de publicación: | 2004 |
| País: | España |
| Institución: | Universidad de Alcalá (UAH) |
| Repositorio: | e_Buah Biblioteca Digital Universidad de Alcalá |
| Idioma: | inglés |
| OAI Identifier: | oai:ebuah.uah.es:10017/4180 |
| Acceso en línea: | http://hdl.handle.net/10017/4180 https://dx.doi.org/10.1002/ejic.200400333 |
| Access Level: | acceso abierto |
| Palabra clave: | Metallocenes Zirconium Insertion Isocyanides Polymerization Ciencia Química inorgánica Science Chemistry, inorganic |
| Sumario: | Alkylation of ansa-zirconocene [Zr{(η5-C5H5)SiMe2(MBI)}Cl2] (MBI = η5-2-Me−C13H7) with MgRCl gave the dimethyl complex [Zr{(η5-C5H5)SiMe2(MBI)}Me2], but unresolvable mixtures containing mono-alkylated compounds were obtained when bulkier alkyls were used. However pure dialkyl complexes [Zr{(η5-C5H5)SiMe2(MBI)}R2] (R = CH2Ph, CH2SiMe3) were easily obtained using K(CH2Ph) and Li(CH2SiMe3) as alkylating agents. Diastereoselective insertion into the MBI-unprotected Zr−R bond was observed when all of these dialkyl complexes were treated with 2,6-xylyl isocyanide to give the iminoacyl compounds [Zr{(η5-C5H5)SiMe2(MBI)}R{CR[η2-N-(2,6-xylyl)]}] (R = Me, CH2Ph, CH2SiMe3). All of the new complexes were characterized by NMR spectroscopy and the X-ray molecular structures of the dibenzyl and the imino-benzyl compounds were determined. The catalytic activity for ethene polymerization and ethene/1-hexene copolymerization of the dichloro zirconocenes [Zr{(η5-C5H5)EMe2(MBI)}Cl2] (E = C, Si), activated with methylalumoxane (MAO), was measured. |
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