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Diastereoselective insertion of isocyanide into the alkyl metal bond of methylbenz[e]indenyl ansa-zirconocene complexes

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Authors
Sebastián Navas, AlfredoUniversity of Alcalá Author; Royo Gracia, PascualUniversity of Alcalá Author; Gómez Sal, Pilar; Ramírez de Arellano, Carmen
Identifiers
Permanent link (URI): http://hdl.handle.net/10017/4180
DOI: 10.1002/ejic.200400333
ISSN: 1099-0682
Publisher
John Wiley & Sons
Date
2004
Affiliation
Universidad de Alcalá. Departamento de Química Inorgánica
Funders
Repsol-YPF
Bibliographic citation
European Journal of Inorganic Chemistry, 2004, v.2004, n.19, p.3814-3821
Keywords
Metallocenes
Zirconium
Insertion
Isocyanides
Polymerization
Project
MAT2001- 1309 (Ministerio de Ciencia y Tecnología)
Document type
info:eu-repo/semantics/article
Version
info:eu-repo/semantics/publishedVersion
Publisher's version
http://dx.doi.org/10.1002/ejic.200400333
Rights
© Wiley, 2004
Access rights
info:eu-repo/semantics/openAccess
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Abstract
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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