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Cationic alkylaluminum-complexed zirconocene hydrides : NMR-spectroscopic identification, crystallographic structure determination, and interconversion with other zirconocene cations

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2011

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Baldwin, Steven M.
Bercaw, John E.
Henling, Lawrence M.
Day, Michael W.

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http://nbn-resolving.de/urn:nbn:de:bsz:352-236619
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https://doi.org/10.1021/ja1050428
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Journal of the American Chemical Society. 2011, 133(6), pp. 1805-1813. ISSN 0002-7863. eISSN 1520-5126. Available under: doi: 10.1021/ja1050428

Zusammenfassung

The ansa-zirconocene complex rac-Me2Si(1-indenyl)2ZrCl2 ((SBI)ZrCl2) reacts with diisobutylaluminum hydride and trityl tetrakis(perfluorophenyl)borate in hydrocarbon solutions to give the cation [(SBI)Zr(μ-H)3(AliBu2)2]+, the identity of which is derived from NMR data and supported by a crystallographic structure determination. Analogous reactions proceed with many other zirconocene dichloride complexes. [(SBI)Zr(μ-H)3(AliBu2)2]+ reacts reversibly with ClAliBu2 to give the dichloro-bridged cation [(SBI)Zr(μ-Cl)2AliBu2]+. Reaction with AlMe3 first leads to mixed-alkyl species [(SBI)Zr(μ-H)3(AlMexiBu2−x)2]+ by exchange of alkyl groups between aluminum centers. At higher AlMe3/Zr ratios, [(SBI)Zr(μ-Me)2AlMe2]+, a constituent of methylalumoxane-activated catalyst systems, is formed in an equilibrium, in which the hydride cation [(SBI)Zr(μ-H)3(AlR2)2]+ strongly predominates at comparable HAliBu2 and AlMe3 concentrations, thus implicating the presence of this hydride cation in olefin polymerization catalyst systems.

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540 Chemie

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ISO 690BALDWIN, Steven M., John E. BERCAW, Lawrence M. HENLING, Michael W. DAY, Hans-Herbert BRINTZINGER, 2011. Cationic alkylaluminum-complexed zirconocene hydrides : NMR-spectroscopic identification, crystallographic structure determination, and interconversion with other zirconocene cations. In: Journal of the American Chemical Society. 2011, 133(6), pp. 1805-1813. ISSN 0002-7863. eISSN 1520-5126. Available under: doi: 10.1021/ja1050428
BibTex
@article{Baldwin2011-02-16Catio-23661,
  year={2011},
  doi={10.1021/ja1050428},
  title={Cationic alkylaluminum-complexed zirconocene hydrides : NMR-spectroscopic identification, crystallographic structure determination, and interconversion with other zirconocene cations},
  number={6},
  volume={133},
  issn={0002-7863},
  journal={Journal of the American Chemical Society},
  pages={1805--1813},
  author={Baldwin, Steven M. and Bercaw, John E. and Henling, Lawrence M. and Day, Michael W. and Brintzinger, Hans-Herbert}
}
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    <dcterms:abstract xml:lang="eng">The ansa-zirconocene complex rac-Me&lt;sub&gt;2&lt;/sub&gt;Si(1-indenyl)&lt;sub&gt;2&lt;/sub&gt;ZrCl&lt;sub&gt;2&lt;/sub&gt; ((SBI)ZrCl&lt;sub&gt;2&lt;/sub&gt;) reacts with diisobutylaluminum hydride and trityl tetrakis(perfluorophenyl)borate in hydrocarbon solutions to give the cation [(SBI)Zr(μ-H)&lt;sub&gt;3&lt;/sub&gt;(AliBu&lt;sub&gt;2&lt;/sub&gt;)&lt;sub&gt;2&lt;/sub&gt;]&lt;sup&gt;+&lt;/sup&gt;, the identity of which is derived from NMR data and supported by a crystallographic structure determination. Analogous reactions proceed with many other zirconocene dichloride complexes. [(SBI)Zr(μ-H)&lt;sup&gt;3&lt;/sup&gt;(AliBu&lt;sub&gt;2&lt;/sub&gt;)&lt;sub&gt;2&lt;/sub&gt;]&lt;sup&gt;+&lt;/sup&gt; reacts reversibly with ClAliBu&lt;sub&gt;2&lt;/sub&gt; to give the dichloro-bridged cation [(SBI)Zr(μ-Cl)&lt;sub&gt;2&lt;/sub&gt;AliBu&lt;sub&gt;2&lt;/sub&gt;]&lt;sup&gt;+&lt;/sup&gt;. Reaction with AlMe&lt;sub&gt;3&lt;/sub&gt; first leads to mixed-alkyl species [(SBI)Zr(μ-H)&lt;sub&gt;3&lt;/sub&gt;(AlMexiBu&lt;sub&gt;2&lt;/sub&gt;−x)&lt;sub&gt;2&lt;/sub&gt;]&lt;sup&gt;+&lt;/sup&gt; by exchange of alkyl groups between aluminum centers. At higher AlMe&lt;sub&gt;3&lt;/sub&gt;/Zr ratios, [(SBI)Zr(μ-Me)&lt;sub&gt;2&lt;/sub&gt;AlMe&lt;sub&gt;2&lt;/sub&gt;]&lt;sup&gt;+&lt;/sup&gt;, a constituent of methylalumoxane-activated catalyst systems, is formed in an equilibrium, in which the hydride cation [(SBI)Zr(μ-H)&lt;sub&gt;3&lt;/sub&gt;(AlR&lt;sub&gt;2&lt;/sub&gt;)&lt;sub&gt;2&lt;/sub&gt;]&lt;sup&gt;+&lt;/sup&gt; strongly predominates at comparable HAliBu&lt;sub&gt;2&lt;/sub&gt; and AlMe&lt;sub&gt;3&lt;/sub&gt; concentrations, thus implicating the presence of this hydride cation in olefin polymerization catalyst systems.</dcterms:abstract>
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    <dc:contributor>Day, Michael W.</dc:contributor>
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