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Selective Dimerization of γ-Branched α-Olefins in the Presence of C2v Group-4 Metallocene-Based Catalysts

✍ Scribed by Antonella C. Boccia; Chiara Costabile; Stefania Pragliola; Pasquale Longo

Book ID: 102483990
Publisher: John Wiley and Sons
Year: 2004
Tongue: English
Weight: 144 KB
Volume: 205
Category: Article
ISSN: 1022-1352
DOI: 10.1002/macp.200400174

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✦ Synopsis

Abstract

Summary: The oligomerization of γ‐branched α‐olefins in the presence of catalytic systems based on group‐4 metallocenes with C~2__v__~ symmetry has been investigated. The highest reactivity was obtained by using dimethylsilyl‐bis(cyclopentadienyl)zirconium‐dichloride activated by methylaluminoxane. Highly regioregular dimers were selectively obtained for hindered γ‐branched monomers, while the less hindered ones produced higher molecular weight oligomers. A molecular modeling approach was used to rationalize the experimental results. In fact, a decrease in the β‐hydrogen elimination barrier and an increase in the insertion barrier with the monomer bulkiness were calculated.

General structure of the obtained dimers.

magnified imageGeneral structure of the obtained dimers.

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