Publikation:

The origin of living polymerization with an o-fluorinated catalyst : NMR spectroscopic characterization of chain-carrying species

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2012

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Talsi, Evgenii P.
Bryliakov, Konstantin P.

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http://nbn-resolving.de/urn:nbn:de:bsz:352-187027
DOI (zitierfähiger Link)
https://doi.org/10.1002/chem.201102408
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Urheberrechtlich geschützt

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Open Access Green

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Chemie: Publikationen
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Published

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Chemistry - A European Journal. 2012, 18(3), pp. 848-856. ISSN 0947-6539. eISSN 1521-3765. Available under: doi: 10.1002/chem.201102408

Zusammenfassung

To characterize the origin of living polymerization with nonmetallocene titanium-based catalysts containing o-fluoroaryl substituents, ethene polymerization by an o-fluorinated bis(enolatoimine) titanium catalyst and its nonfluorinated counterpart has been studied by multinuclear NMR spectroscopy by using methylaluminoxane (MAO) or AlMe3/CPh3B(C6F5)4 as activators. Formation of ion pairs of the type [TiL2Me][MeMAO] and [TiL2Me][B(C6F5)4] has been observed for both catalysts. These ion pairs react with ethene to afford the chain-propagating species [TiL2P][MeMAO] and [TiL2P][B(C6F5)4], respectively (P=growing polymeryl chain). For the o-F-substituted catalyst species of the second type, NMR spectroscopy provides evidence that the o-F substituents interact with the metal center. This interaction is proposed to keep the polymerization catalysis living by suppressing chain transfer to AlMe3 and β-hydrogen transfer processes.

Zusammenfassung in einer weiteren Sprache

Fachgebiet (DDC)
540 Chemie

Schlagwörter

fluorine, ion pairs, living polymerization, reaction mechanisms, titanium

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ISO 690MÖLLER, Heiko M., Moritz C. BAIER, Stefan MECKING, Evgenii P. TALSI, Konstantin P. BRYLIAKOV, 2012. The origin of living polymerization with an o-fluorinated catalyst : NMR spectroscopic characterization of chain-carrying species. In: Chemistry - A European Journal. 2012, 18(3), pp. 848-856. ISSN 0947-6539. eISSN 1521-3765. Available under: doi: 10.1002/chem.201102408
BibTex
@article{Moller2012-01-16origi-18702,
  year={2012},
  doi={10.1002/chem.201102408},
  title={The origin of living polymerization with an o-fluorinated catalyst : NMR spectroscopic characterization of chain-carrying species},
  number={3},
  volume={18},
  issn={0947-6539},
  journal={Chemistry - A European Journal},
  pages={848--856},
  author={Möller, Heiko M. and Baier, Moritz C. and Mecking, Stefan and Talsi, Evgenii P. and Bryliakov, Konstantin P.}
}
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    <dcterms:abstract xml:lang="eng">To characterize the origin of living polymerization with nonmetallocene titanium-based catalysts containing o-fluoroaryl substituents, ethene polymerization by an o-fluorinated bis(enolatoimine) titanium catalyst and its nonfluorinated counterpart has been studied by multinuclear NMR spectroscopy by using methylaluminoxane (MAO) or AlMe&lt;sub&gt;3&lt;/sub&gt;/CPh&lt;sub&gt;3&lt;/sub&gt;B(C&lt;sub&gt;6&lt;/sub&gt;F&lt;sub&gt;5&lt;/sub&gt;)&lt;sub&gt;4&lt;/sub&gt; as activators. Formation of ion pairs of the type [TiL&lt;sub&gt;2&lt;/sub&gt;Me][MeMAO] and [TiL&lt;sub&gt;2&lt;/sub&gt;Me][B(C&lt;sub&gt;6&lt;/sub&gt;F&lt;sub&gt;5&lt;/sub&gt;)&lt;sub&gt;4&lt;/sub&gt;] has been observed for both catalysts. These ion pairs react with ethene to afford the chain-propagating species [TiL&lt;sub&gt;2&lt;/sub&gt;P][MeMAO] and [TiL&lt;sub&gt;2&lt;/sub&gt;P][B(C&lt;sub&gt;6&lt;/sub&gt;F&lt;sub&gt;5&lt;/sub&gt;)&lt;sub&gt;4&lt;/sub&gt;], respectively (P=growing polymeryl chain). For the o-F-substituted catalyst species of the second type, NMR spectroscopy provides evidence that the o-F substituents interact with the metal center. This interaction is proposed to keep the polymerization catalysis living by suppressing chain transfer to AlMe&lt;sub&gt;3&lt;/sub&gt; and β-hydrogen transfer processes.</dcterms:abstract>
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