Publikation:

Methylalumoxane (MAO)-derived MeMAO− anions in zirconocene-based polymerization catalyst systems – a UV-Vis spectroscopic study

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2006

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Wieser, Ulrich
Schaper, Frank

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http://nbn-resolving.de/urn:nbn:de:bsz:352-236741
DOI (zitierfähiger Link)
https://doi.org/10.1002/masy.200690068
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Chemie: Publikationen
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Published

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Macromolecular Symposia. 2006, 236(1), pp. 63-68. ISSN 1022-1360. eISSN 1521-3900. Available under: doi: 10.1002/masy.200690068

Zusammenfassung

Reaction of Me2Si(Ind)2ZrCl2 with excess methylalumoxane (MAO) gives rise to ion pairs containing zirconocenium cations of the type [Me2Si(Ind)2ZrMe]+ in contact with two types of anions, MeMAOA− and MeMAOB−, which differ in their coordinative strengths: More strongly coherent contact-ion pairs [Me2Si(Ind)2 ZrMe+**MeMAOB−] are converted by a sufficiently high excess of MAO to more easily separable contact-ion pairs [Me2Si(Ind)2ZrMe+**MeMAOA−], which react with AlMe3 to form the outer-sphere ion pairs [Me2Si(Ind)2Zr(µ-Me)2AlMe2]+ MeMAOA−, and are likely to be required also for the formation of the olefin-containing reaction complexes responsible for catalytic activity.

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Fachgebiet (DDC)
540 Chemie

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Metallocene catalysts, methylalumoxane, polymerization catalysis, reaction intermediates, UV-vis spectroscopy

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ISO 690WIESER, Ulrich, Frank SCHAPER, Hans-Herbert BRINTZINGER, 2006. Methylalumoxane (MAO)-derived MeMAO− anions in zirconocene-based polymerization catalyst systems – a UV-Vis spectroscopic study. In: Macromolecular Symposia. 2006, 236(1), pp. 63-68. ISSN 1022-1360. eISSN 1521-3900. Available under: doi: 10.1002/masy.200690068
BibTex
@article{Wieser2006Methy-23674,
  year={2006},
  doi={10.1002/masy.200690068},
  title={Methylalumoxane (MAO)-derived MeMAO<sup>−</sup> anions in zirconocene-based polymerization catalyst systems – a UV-Vis spectroscopic study},
  number={1},
  volume={236},
  issn={1022-1360},
  journal={Macromolecular Symposia},
  pages={63--68},
  author={Wieser, Ulrich and Schaper, Frank and Brintzinger, Hans-Herbert}
}
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    <dcterms:abstract xml:lang="eng">Reaction of 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; with excess methylalumoxane (MAO) gives rise to ion pairs containing zirconocenium cations of the type [Me&lt;sub&gt;2&lt;/sub&gt;Si(Ind)&lt;sub&gt;2&lt;/sub&gt;ZrMe]&lt;sup&gt;+&lt;/sup&gt; in contact with two types of anions, MeMAO&lt;sub&gt;A&lt;/sub&gt;&lt;sup&gt;−&lt;/sup&gt; and MeMAO&lt;sub&gt;B&lt;/sub&gt;&lt;sup&gt;−&lt;/sup&gt;, which differ in their coordinative strengths: More strongly coherent contact-ion pairs [Me&lt;sub&gt;2&lt;/sub&gt;Si(Ind)&lt;sub&gt;2&lt;/sub&gt; ZrMe&lt;sup&gt;+&lt;/sup&gt;**MeMAOB&lt;sup&gt;−&lt;/sup&gt;] are converted by a sufficiently high excess of MAO to more easily separable contact-ion pairs [Me&lt;sub&gt;2&lt;/sub&gt;Si(Ind)&lt;sub&gt;2&lt;/sub&gt;ZrMe&lt;sup&gt;+&lt;/sup&gt;**MeMAOA&lt;sup&gt;−&lt;/sup&gt;], which react with AlMe&lt;sub&gt;3&lt;/sub&gt; to form the outer-sphere ion pairs [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; MeMAO&lt;sub&gt;A&lt;/sub&gt;&lt;sup&gt;−&lt;/sup&gt;, and are likely to be required also for the formation of the olefin-containing reaction complexes responsible for catalytic activity.</dcterms:abstract>
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