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Updated: Jul 19, 2026

Accessing Valuable Ligand Supports for Transition Metals: A Modified, Intermediate Scale Preparation of 1,2,3,4,5-Pentamethylcyclopentadiene
Published on: March 20, 2017
Ansa-metallocene polymerization catalysts derived from [2+2]cycloaddition reactions of
Jan Paradies1, Gerald Kehr, Roland Fröhlich
1Organisch-Chemisches Institut der Universität Münster, Corrensstrasse 40, 48149 Münster, Germany.
Abstract:
Bis(1-methylethenyl-cyclopentadienyl)zirconium dichloride (7a) was prepared by a fulvene route. Photolysis at 0 degrees C with Pyrex-filtered UV light resulted in a rapid and complete intramolecular [2+2]cycloaddition reaction to yield the corresponding cyclobutylene-bridged ansa-zirconocene dichloride isomer (8a). This is one of the rare examples of an organic functional group chemistry that leads to carbon-carbon coupling at the framework of an intact sensitive group 4 bent metallocene complex. More sterically hindered open metallocenes that bear bulky isopropyl or tert-butyl substituents at their Cp rings in addition to the active 1-methylethenyl functional group undergo the photochemical ansa-metallocene ring closure reaction equally facile. The metallocene systems used and obtained in this study have served as transition metal components for the generation of active metallocene propene polymerization catalysts.
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