Synthesis, structure, and ethene polymerisation catalysis of 1- or 2-silyl substituted bis[indenyl]zirconium(IV) dichlorides

Dalton Transactions : an International Journal of Inorganic Chemistry
Andreas C MöllerJürgen Kopf

Abstract

The systematic syntheses of 1- and 2-substituted silylindenes, with a wide variety of substitution patterns on the silyl moiety, and their corresponding zirconocene dichlorides are presented. The rac- and meso-diastereomers of the 1-substituted zirconocene dichlorides can in most cases be separated. Instable zirconocenes were observed for certain substitution patterns. Two of the obtained zirconocene dichlorides, bis[2-(dimethylsilyl)indenyl]zirconium dichloride (4a) and bis[2-(trimethylsilyl)indenyl]zirconium dichloride (4b), were characterised by single crystal X-ray diffraction. On the basis of DFT results, the two compounds are geometrically similar, i.e. the additional methyl group on the silyl moiety only affects the conformational energy profile. Differences in their catalyst performance in the homopolymerisation studies with ethane are thus attributed to conformational control. For the remaining complexes, sterically less demanding silyl groups seem to be favoured with respect to the catalyst performance. All the 2-isomers have lower polymerisation activities than the unsubstituted bis[indenyl]zirconium dichloride/MAO system. Curiously, the rac-bis[1-(dimethylphenylsilyl)indenyl]zirconium dichloride/MAO system is found ...Continue Reading

References

Sep 26, 2002·Journal of the American Chemical Society·Takeaki IwamotoMitsuo Kira
Dec 20, 2002·Angewandte Chemie·Vincenzo BusicoValeria Van Axel Castelli
Aug 1, 1988·Journal of the American Chemical Society·J A EwenJ D Ferrara

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Citations

Aug 6, 2014·The Journal of Organic Chemistry·Hidenori KinoshitaKatsukiyo Miura
Apr 21, 2006·Dalton Transactions : an International Journal of Inorganic Chemistry·Andreas C MöllerTanja Seraidaris
Aug 8, 2019·Chemical Communications : Chem Comm·Xin TaoGerhard Erker

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