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Issue 10, 2004
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Synthesis, structure, and ethene polymerisation catalysis of 1- or 2-silyl substituted bis[indenyl]zirconium(IV) dichlorides

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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 to be the most active catalyst in ethene homopolymerisations.

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

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Publication details

The article was received on 13 Jan 2004, accepted on 24 Mar 2004 and first published on 21 Apr 2004


Article type: Paper
DOI: 10.1039/B400505H
Citation: Dalton Trans., 2004,0, 1578-1589
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    Synthesis, structure, and ethene polymerisation catalysis of 1- or 2-silyl substituted bis[indenyl]zirconium(IV) dichlorides

    A. C. Möller, R. H. Heyn, R. Blom, O. Swang, C. H. Görbitz and J. Kopf, Dalton Trans., 2004, 0, 1578
    DOI: 10.1039/B400505H

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