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Modification of methylaluminoxane-activated ansa-zirconocene catalysts with triisobutylaluminum-transformations of reactive cations studied by NMR spectroscopy

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Babushkin_236687.pdf
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2007

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Babushkin, Dmitrii E.

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http://nbn-resolving.de/urn:nbn:de:bsz:352-236687
DOI (zitierfähiger Link)
https://doi.org/10.1002/chem.200601801
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Chemistry - A European Journal. 2007, 13(18), pp. 5294-5299. ISSN 0947-6539. eISSN 1521-3765. Available under: doi: 10.1002/chem.200601801

Zusammenfassung

When triisobutylaluminum (AliBu3) is added to solutions containing methylaluminoxane (MAO) and rac-[Me2Si(ind)2ZrCl2] (ind: indenyl) in C6D6, NMR spectra show that methyl-bridged mixed-alkylaluminum dimers Al(μ-Me)2Me4−xiBux predominate. These dimers react with MAO under partial transfer of isobutyl groups and induce a conversion of the initially prevailing cationic trimethylaluminum adduct rac-[Me2Si(ind)2Zr(μ-Me)2AlMe2+] to rac-[Me2Si(ind)2Zr(μ-Me)2AlMeiBu+] and rac-[Me2Si(ind)2Zr(μ-Me)2AliBu2+]. These species are unstable and release isobutene under formation of zirconocene hydrides.

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Fachgebiet (DDC)
540 Chemie

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Aluminum alkyls, metallocenes, methylaluminoxane, polymerization, structure–activity relationships

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ISO 690BABUSHKIN, Dmitrii E., Hans-Herbert BRINTZINGER, 2007. Modification of methylaluminoxane-activated ansa-zirconocene catalysts with triisobutylaluminum-transformations of reactive cations studied by NMR spectroscopy. In: Chemistry - A European Journal. 2007, 13(18), pp. 5294-5299. ISSN 0947-6539. eISSN 1521-3765. Available under: doi: 10.1002/chem.200601801
BibTex
@article{Babushkin2007Modif-23668,
  year={2007},
  doi={10.1002/chem.200601801},
  title={Modification of methylaluminoxane-activated ansa-zirconocene catalysts with triisobutylaluminum-transformations of reactive cations studied by NMR spectroscopy},
  number={18},
  volume={13},
  issn={0947-6539},
  journal={Chemistry - A European Journal},
  pages={5294--5299},
  author={Babushkin, Dmitrii E. and Brintzinger, Hans-Herbert}
}
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    <dcterms:abstract xml:lang="eng">When triisobutylaluminum (AliBu&lt;sub&gt;3&lt;/sub&gt;) is added to solutions containing methylaluminoxane (MAO) and rac-[Me&lt;sub&gt;2&lt;/sub&gt;Si(ind)&lt;sub&gt;2&lt;/sub&gt;ZrCl&lt;sub&gt;2&lt;/sub&gt;] (ind: indenyl) in C&lt;sub&gt;6&lt;/sub&gt;D&lt;sub&gt;6&lt;/sub&gt;, NMR spectra show that methyl-bridged mixed-alkylaluminum dimers Al(μ-Me)&lt;sub&gt;2&lt;/sub&gt;Me&lt;sub&gt;4&lt;/sub&gt;−xiBux predominate. These dimers react with MAO under partial transfer of isobutyl groups and induce a conversion of the initially prevailing cationic trimethylaluminum adduct rac-[Me&lt;sub&gt;2&lt;/sub&gt;Si(ind)&lt;sub&gt;2&lt;/sub&gt;Zr(μ-Me)&lt;sub&gt;2&lt;/sub&gt;AlMe&lt;sub&gt;2&lt;/sub&gt;&lt;sup&gt;+&lt;/sup&gt;] to rac-[Me&lt;sub&gt;2&lt;/sub&gt;Si(ind)&lt;sub&gt;2&lt;/sub&gt;Zr(μ-Me)&lt;sub&gt;2&lt;/sub&gt;AlMeiBu&lt;sup&gt;+&lt;/sup&gt;] and rac-[Me&lt;sub&gt;2&lt;/sub&gt;Si(ind)&lt;sub&gt;2&lt;/sub&gt;Zr(μ-Me)&lt;sub&gt;2&lt;/sub&gt;AliBu&lt;sub&gt;2&lt;/sub&gt;&lt;sup&gt;+&lt;/sup&gt;]. These species are unstable and release isobutene under formation of zirconocene hydrides.</dcterms:abstract>
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