rac-Me 2 Si(2-Me-4-t-Bu-C 5 H 2) 2 ZrMe + : an alkyl zirconocenium cation stabilized by steric shielding against interaction with ancillary ligands

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2005
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Schröder, Lars
Babushkin, Dmitrii E.
Fischer, David
Mülhaupt, Rolf
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Organometallics. 2005, 24(5), pp. 867-871. ISSN 0276-7333. eISSN 1520-6041. Available under: doi: 10.1021/om049139z
Zusammenfassung

The sterically shielded cation rac-Me2Si(2-Me-4-t-Bu-C5H2)2ZrMe+, generated by reaction of rac-Me2Si(2-Me-4-t-Bu-C5H2)2ZrMe2 with methylalumoxane (MAO) or with dimethylanilinium or trityl perfluorotetraphenylborate, differs from other, more open zirconocene methyl cations in that it does not form the symmetric AlMe3 adduct rac-Me2Si(2-Me-4-t-Bu-C5H2)2Zr(μ-Me)2AlMe2+. Instead, the unsymmetric ternary adduct rac-Me2Si(2-Me-4-t-Bu-C5H2)2ZrMe(μ-Me)AlMe3−NMe2Ph+ is formed in the presence of dimethylaniline and trimethylaluminum. UV/vis and 1H NMR characteristics of hydrocarbon solutions containing rac-Me2Si(2-Me-4-t-Bu-C5H2)2ZrMe+***B(C6F5)4- or rac-Me2Si(2-Me-4-t-Bu-C5H2)2ZrMe+***MAOMe- indicate that cation−anion association in these ion pairs is unusually weak.

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ISO 690SCHRÖDER, Lars, Hans-Herbert BRINTZINGER, Dmitrii E. BABUSHKIN, David FISCHER, Rolf MÜLHAUPT, 2005. rac-Me 2 Si(2-Me-4-t-Bu-C 5 H 2) 2 ZrMe + : an alkyl zirconocenium cation stabilized by steric shielding against interaction with ancillary ligands. In: Organometallics. 2005, 24(5), pp. 867-871. ISSN 0276-7333. eISSN 1520-6041. Available under: doi: 10.1021/om049139z
BibTex
@article{Schroder2005racMe-23720,
  year={2005},
  doi={10.1021/om049139z},
  title={rac-Me 2 Si(2-Me-4-t-Bu-C 5 H 2) 2 ZrMe + : an alkyl zirconocenium cation stabilized by steric shielding against interaction with ancillary ligands},
  number={5},
  volume={24},
  issn={0276-7333},
  journal={Organometallics},
  pages={867--871},
  author={Schröder, Lars and Brintzinger, Hans-Herbert and Babushkin, Dmitrii E. and Fischer, David and Mülhaupt, Rolf}
}
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    <dcterms:abstract xml:lang="eng">The sterically shielded cation rac-Me&lt;sub&gt;2&lt;/sub&gt;Si(2-Me-4-t-Bu-C&lt;sub&gt;5&lt;/sub&gt;H&lt;sub&gt;2&lt;/sub&gt;)&lt;sub&gt;2&lt;/sub&gt;ZrMe&lt;sup&gt;+&lt;/sup&gt;, generated by reaction of rac-Me&lt;sub&gt;2&lt;/sub&gt;Si(2-Me-4-t-Bu-C&lt;sub&gt;5&lt;/sub&gt;H&lt;sub&gt;2&lt;/sub&gt;)&lt;sub&gt;2&lt;/sub&gt;ZrMe&lt;sub&gt;2&lt;/sub&gt; with methylalumoxane (MAO) or with dimethylanilinium or trityl perfluorotetraphenylborate, differs from other, more open zirconocene methyl cations in that it does not form the symmetric AlMe&lt;sub&gt;3&lt;/sub&gt; adduct rac-Me&lt;sub&gt;2&lt;/sub&gt;Si(2-Me-4-t-Bu-C&lt;sub&gt;5&lt;/sub&gt;H&lt;sub&gt;2&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;. Instead, the unsymmetric ternary adduct rac-Me&lt;sub&gt;2&lt;/sub&gt;Si(2-Me-4-t-Bu-C&lt;sub&gt;5&lt;/sub&gt;H&lt;sub&gt;2&lt;/sub&gt;)&lt;sub&gt;2&lt;/sub&gt;ZrMe(μ-Me)AlMe&lt;sub&gt;3&lt;/sub&gt;−NMe&lt;sub&gt;2&lt;/sub&gt;Ph&lt;sup&gt;+&lt;/sup&gt; is formed in the presence of dimethylaniline and trimethylaluminum. UV/vis and &lt;sup&gt;1&lt;/sup&gt;H NMR characteristics of hydrocarbon solutions containing rac-Me&lt;sub&gt;2&lt;/sub&gt;Si(2-Me-4-t-Bu-C&lt;sub&gt;5&lt;/sub&gt;H&lt;sub&gt;2&lt;/sub&gt;)&lt;sub&gt;2&lt;/sub&gt;ZrMe&lt;sup&gt;+&lt;/sup&gt;***B(C&lt;sub&gt;6&lt;/sub&gt;F&lt;sub&gt;5&lt;/sub&gt;)4- or rac-Me&lt;sub&gt;2&lt;/sub&gt;Si(2-Me-4-t-Bu-C&lt;sub&gt;5&lt;/sub&gt;H&lt;sub&gt;2&lt;/sub&gt;)&lt;sub&gt;2&lt;/sub&gt;ZrMe&lt;sup&gt;+&lt;/sup&gt;***MAOMe&lt;sup&gt;-&lt;/sup&gt; indicate that cation−anion association in these ion pairs is unusually weak.</dcterms:abstract>
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