Binuclear zirconocene cations with μ-CH3-bridges in homogeneous Ziegler-Natta catalyst systems

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1996
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Beck, Stefan
Prosenc, Marc-Heinrich
Goretzki, Ralf
Herfert, Norbert
Fink, Gerhard
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http://nbn-resolving.de/urn:nbn:de:bsz:352-239201
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https://doi.org/10.1016/1381-1169(96)00168-9
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Journal of Molecular Catalysis A: Chemical. 1996, 111(1-2), pp. 67-79. ISSN 1381-1169. Available under: doi: 10.1016/1381-1169(96)00168-9
Zusammenfassung

Binuclear zirconocene cations are observed by 1H-NMR in C6D6 solutions containing B(C6F5)3 and an excess of a zirconocene dimethyl complex. The CH3-bridged cation [((C5H5)2ZrCH3)2(μ-CH3)]+, solvent-separated from the anion H3CB(C6F5)−3, is present in equilibrium with (C5H5)2Zr(CH3)2 and the mononuclear ion pair [(C5H5)2ZrCH+3***H3CB(C6F5)−3]; in more concentrated solutions, a binuclear ion pair [((C5H5)2ZrCH3)2(μ-CH3)+***H3CB(C6F5)−3] is the dominant species. Similar equilibria are observed in C6D6 solutions containing B(C6F5)3 and (CH3)4C2(C5H4)2Zr(CH3)2, (CH3)2Si(C5H4)2Zr(CH3)2 or rac-(CH3)2Si(indenyl)2Zr(CH3)2. Complexes with sterically more demanding ligands, such as (C5(CH3)5)2Zr(CH3)2 or rac-(CH3)2Si(2-methyl-benz[e]indenyl)2Zr(CH3)2 do not form any binuclear species under these conditions. In the catalyst system rac-(CH3)2Si(indenyl)2Zr(CH3)2Bu3NH+B(C6F5)−4, activities for the polymerization of propene increase with excess of the dimethyl zirconocene complex. This effect is due in part to a sacrifice of some dimethyl zirconocene for the removal of impurities from the catalyst system and in part to a stabilization of the catalyst in the form of the binuclear cation [((CH3)2Si(indenyl)2ZrCH3)2(μ-CH3)]+. The latter appears to act, in the presence of propene, as a source of the mononuclear cation [(CH3)2Si(indenyl)2ZrCH3(C3H6)]+, rather than as a polymerization catalyst by itself.

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540 Chemie
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NMR, Ziegler-Natta, zirconocene
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ISO 690BECK, Stefan, Marc-Heinrich PROSENC, Hans-Herbert BRINTZINGER, Ralf GORETZKI, Norbert HERFERT, Gerhard FINK, 1996. Binuclear zirconocene cations with μ-CH3-bridges in homogeneous Ziegler-Natta catalyst systems. In: Journal of Molecular Catalysis A: Chemical. 1996, 111(1-2), pp. 67-79. ISSN 1381-1169. Available under: doi: 10.1016/1381-1169(96)00168-9
BibTex
@article{Beck1996Binuc-23920,
  year={1996},
  doi={10.1016/1381-1169(96)00168-9},
  title={Binuclear zirconocene cations with μ-CH<sub>3</sub>-bridges in homogeneous Ziegler-Natta catalyst systems},
  number={1-2},
  volume={111},
  issn={1381-1169},
  journal={Journal of Molecular Catalysis A: Chemical},
  pages={67--79},
  author={Beck, Stefan and Prosenc, Marc-Heinrich and Brintzinger, Hans-Herbert and Goretzki, Ralf and Herfert, Norbert and Fink, Gerhard}
}
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    <dcterms:abstract xml:lang="eng">Binuclear zirconocene cations are observed by &lt;sup&gt;1&lt;/sup&gt;H-NMR in C&lt;sub&gt;6&lt;/sub&gt;D&lt;sub&gt;6&lt;/sub&gt; solutions containing B(C&lt;sub&gt;6&lt;/sub&gt;F&lt;sub&gt;5&lt;/sub&gt;)&lt;sub&gt;3&lt;/sub&gt; and an excess of a zirconocene dimethyl complex. The CH&lt;sub&gt;3&lt;/sub&gt;-bridged cation [((C&lt;sub&gt;5&lt;/sub&gt;H&lt;sub&gt;5&lt;/sub&gt;)&lt;sub&gt;2&lt;/sub&gt;ZrCH&lt;sub&gt;3&lt;/sub&gt;)&lt;sub&gt;2&lt;/sub&gt;(μ-CH&lt;sub&gt;3&lt;/sub&gt;)]&lt;sup&gt;+&lt;/sup&gt;, solvent-separated from the anion H3CB(C&lt;sub&gt;6&lt;/sub&gt;F&lt;sub&gt;5&lt;/sub&gt;)&lt;sup&gt;−&lt;/sup&gt;&lt;sub&gt;3&lt;/sub&gt;, is present in equilibrium with (C&lt;sub&gt;5&lt;/sub&gt;H&lt;sub&gt;5&lt;/sub&gt;)&lt;sub&gt;2&lt;/sub&gt;Zr(CH&lt;sub&gt;3&lt;/sub&gt;)&lt;sub&gt;2&lt;/sub&gt; and the mononuclear ion pair [(C&lt;sub&gt;5&lt;/sub&gt;H&lt;sub&gt;5&lt;/sub&gt;)&lt;sub&gt;2&lt;/sub&gt;ZrCH&lt;sup&gt;+&lt;/sup&gt;&lt;sub&gt;3&lt;/sub&gt;***H&lt;sub&gt;3&lt;/sub&gt;CB(C&lt;sub&gt;6&lt;/sub&gt;F&lt;sub&gt;5&lt;/sub&gt;)&lt;sup&gt;−&lt;/sup&gt;&lt;sub&gt;3&lt;/sub&gt;]; in more concentrated solutions, a binuclear ion pair [((C&lt;sub&gt;5&lt;/sub&gt;H&lt;sub&gt;5&lt;/sub&gt;)&lt;sub&gt;2&lt;/sub&gt;ZrCH&lt;sub&gt;3&lt;/sub&gt;)&lt;sub&gt;2&lt;/sub&gt;(μ-CH&lt;sub&gt;3&lt;/sub&gt;)&lt;sup&gt;+&lt;/sup&gt;***H&lt;sub&gt;3&lt;/sub&gt;CB(C&lt;sub&gt;6&lt;/sub&gt;F&lt;sub&gt;5&lt;/sub&gt;)&lt;sup&gt;−&lt;/sup&gt;&lt;sub&gt;3&lt;/sub&gt;] is the dominant species. Similar equilibria are observed in C&lt;sub&gt;6&lt;/sub&gt;D&lt;sub&gt;6&lt;/sub&gt; solutions containing B(C&lt;sub&gt;6&lt;/sub&gt;F&lt;sub&gt;5&lt;/sub&gt;)&lt;sub&gt;3&lt;/sub&gt; and (CH&lt;sub&gt;3&lt;/sub&gt;)&lt;sub&gt;4&lt;/sub&gt;C&lt;sub&gt;2&lt;/sub&gt;(C&lt;sub&gt;5&lt;/sub&gt;H&lt;sub&gt;4&lt;/sub&gt;)&lt;sub&gt;2&lt;/sub&gt;Zr(CH&lt;sub&gt;3&lt;/sub&gt;)&lt;sub&gt;2&lt;/sub&gt;, (CH&lt;sub&gt;3&lt;/sub&gt;)&lt;sub&gt;2&lt;/sub&gt;Si(C&lt;sub&gt;5&lt;/sub&gt;H&lt;sub&gt;4&lt;/sub&gt;)&lt;sub&gt;2&lt;/sub&gt;Zr(CH&lt;sub&gt;3&lt;/sub&gt;)&lt;sub&gt;2&lt;/sub&gt; or rac-(CH&lt;sub&gt;3&lt;/sub&gt;)&lt;sub&gt;2&lt;/sub&gt;Si(indenyl)&lt;sub&gt;2&lt;/sub&gt;Zr(CH&lt;sub&gt;3&lt;/sub&gt;)&lt;sub&gt;2&lt;/sub&gt;. Complexes with sterically more demanding ligands, such as (C&lt;sub&gt;5&lt;/sub&gt;(CH&lt;sub&gt;3&lt;/sub&gt;)&lt;sub&gt;5&lt;/sub&gt;)&lt;sub&gt;2&lt;/sub&gt;Zr(CH&lt;sub&gt;3&lt;/sub&gt;)&lt;sub&gt;2&lt;/sub&gt; or rac-(CH&lt;sub&gt;3&lt;/sub&gt;)&lt;sub&gt;2&lt;/sub&gt;Si(2-methyl-benz[e]indenyl)&lt;sub&gt;2&lt;/sub&gt;Zr(CH&lt;sub&gt;3&lt;/sub&gt;)&lt;sub&gt;2&lt;/sub&gt; do not form any binuclear species under these conditions. In the catalyst system rac-(CH&lt;sub&gt;3&lt;/sub&gt;)&lt;sub&gt;2&lt;/sub&gt;Si(indenyl)&lt;sub&gt;2&lt;/sub&gt;Zr(CH&lt;sub&gt;3&lt;/sub&gt;)&lt;sub&gt;2&lt;/sub&gt;Bu&lt;sub&gt;3&lt;/sub&gt;NH&lt;sup&gt;+&lt;/sup&gt;B(C&lt;sub&gt;6&lt;/sub&gt;F&lt;sub&gt;5&lt;/sub&gt;)&lt;sup&gt;−&lt;/sup&gt;&lt;sub&gt;4&lt;/sub&gt;, activities for the polymerization of propene increase with excess of the dimethyl zirconocene complex. This effect is due in part to a sacrifice of some dimethyl zirconocene for the removal of impurities from the catalyst system and in part to a stabilization of the catalyst in the form of the binuclear cation [((CH&lt;sub&gt;3&lt;/sub&gt;)&lt;sub&gt;2&lt;/sub&gt;Si(indenyl)&lt;sub&gt;2&lt;/sub&gt;ZrCH&lt;sub&gt;3&lt;/sub&gt;)&lt;sub&gt;2&lt;/sub&gt;(μ-CH&lt;sub&gt;3&lt;/sub&gt;)]&lt;sup&gt;+&lt;/sup&gt;. The latter appears to act, in the presence of propene, as a source of the mononuclear cation [(CH&lt;sub&gt;3&lt;/sub&gt;)&lt;sub&gt;2&lt;/sub&gt;Si(indenyl)&lt;sub&gt;2&lt;/sub&gt;ZrCH&lt;sub&gt;3&lt;/sub&gt;(C&lt;sub&gt;3&lt;/sub&gt;H&lt;sub&gt;6&lt;/sub&gt;)]&lt;sup&gt;+&lt;/sup&gt;, rather than as a polymerization catalyst by itself.</dcterms:abstract>
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