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Distinct methylalumoxane(MAO)-derived Me–MAO− anions in contact with a zirconocenium cation—a 13C-NMR study

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2006

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Babushkin, Dmitrii E.
Naundorf, Corinna

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http://nbn-resolving.de/urn:nbn:de:bsz:352-236734
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https://doi.org/10.1039/B611028M
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Dalton Transactions. 2006(38), pp. 4539-4544. ISSN 1477-9226. eISSN 1477-9234. Available under: doi: 10.1039/B611028M

Zusammenfassung

Zirconocenium cations of the type [(MeC5H4)2ZrMe]+, formed by excess methylalumoxane (MAO) from (MeC5H4)2ZrCl2 or (MeC5H4)2ZrMe2 with 13C-labelled ring ligands, are found to form ion pairs with two types of anions, Me–MAOA− and Me–MAOB−, which differ in their coordinative strengths: More strongly coherent ion pairs [(MeC5H4)2ZrMe+***Me–MAOB−] are converted to more easily separable ion pairs [(MeC5H4)2ZrMe+***Me–MAOA−] by a sufficient excess of MAO. These react with Al2Me6 to form outer-sphere ion pairs containing the cationic AlMe3 adduct [(MeC5H4)2Zr(µ-Me)2AlMe2]+; formation of the more easily separable ion pairs might be required also for polymerisation catalysis.

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540 Chemie

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ISO 690BABUSHKIN, Dmitrii E., Corinna NAUNDORF, Hans-Herbert BRINTZINGER, 2006. Distinct methylalumoxane(MAO)-derived Me–MAO− anions in contact with a zirconocenium cation—a 13C-NMR study. In: Dalton Transactions. 2006(38), pp. 4539-4544. ISSN 1477-9226. eISSN 1477-9234. Available under: doi: 10.1039/B611028M
BibTex
@article{Babushkin2006-10-14Disti-23673,
  year={2006},
  doi={10.1039/B611028M},
  title={Distinct methylalumoxane(MAO)-derived Me–MAO<sup>−</sup> anions in contact with a zirconocenium cation—a <sup>13</sup>C-NMR study},
  number={38},
  issn={1477-9226},
  journal={Dalton Transactions},
  pages={4539--4544},
  author={Babushkin, Dmitrii E. and Naundorf, Corinna and Brintzinger, Hans-Herbert}
}
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    <dcterms:abstract xml:lang="eng">Zirconocenium cations of the type [(MeC&lt;sub&gt;5&lt;/sub&gt;H&lt;sub&gt;4&lt;/sub&gt;)&lt;sub&gt;2&lt;/sub&gt;ZrMe]&lt;sup&gt;+&lt;/sup&gt;, formed by excess methylalumoxane (MAO) from (MeC&lt;sub&gt;5&lt;/sub&gt;H&lt;sub&gt;4&lt;/sub&gt;)&lt;sub&gt;2&lt;/sub&gt;ZrCl&lt;sub&gt;2&lt;/sub&gt; or (MeC&lt;sub&gt;5&lt;/sub&gt;H&lt;sub&gt;4&lt;/sub&gt;)&lt;sub&gt;2&lt;/sub&gt;ZrMe&lt;sub&gt;2&lt;/sub&gt; with &lt;sup&gt;13&lt;/sup&gt;C-labelled ring ligands, are found to form ion pairs with two types of anions, Me–MAO&lt;sub&gt;A&lt;/sub&gt;&lt;sup&gt;−&lt;/sup&gt; and Me–MAO&lt;sub&gt;B&lt;/sub&gt;&lt;sup&gt;−&lt;/sup&gt;, which differ in their coordinative strengths: More strongly coherent ion pairs [(MeC&lt;sub&gt;5&lt;/sub&gt;H&lt;sub&gt;4&lt;/sub&gt;)&lt;sub&gt;2&lt;/sub&gt;ZrMe&lt;sup&gt;+&lt;/sup&gt;***Me–MAO&lt;sub&gt;B&lt;/sub&gt;&lt;sup&gt;−&lt;/sup&gt;] are converted to more easily separable ion pairs [(MeC&lt;sub&gt;5&lt;/sub&gt;H&lt;sub&gt;4&lt;/sub&gt;)&lt;sub&gt;2&lt;/sub&gt;ZrMe&lt;sup&gt;+&lt;/sup&gt;***Me–MAO&lt;sub&gt;A&lt;/sub&gt;&lt;sup&gt;−&lt;/sup&gt;] by a sufficient excess of MAO. These react with Al&lt;sub&gt;2&lt;/sub&gt;Me&lt;sub&gt;6&lt;/sub&gt; to form outer-sphere ion pairs containing the cationic AlMe&lt;sub&gt;3&lt;/sub&gt; adduct [(MeC&lt;sub&gt;5&lt;/sub&gt;H&lt;sub&gt;4&lt;/sub&gt;)&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;; formation of the more easily separable ion pairs might be required also for polymerisation catalysis.</dcterms:abstract>
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