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

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

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MÖLLER, Heiko, Moritz 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. 18(3), pp. 848-856. ISSN 0947-6539. eISSN 1521-3765. Available under: doi: 10.1002/chem.201102408

@article{Moller2012-01-16origi-18702, title={The origin of living polymerization with an o-fluorinated catalyst : NMR spectroscopic characterization of chain-carrying species}, year={2012}, doi={10.1002/chem.201102408}, number={3}, volume={18}, issn={0947-6539}, journal={Chemistry - A European Journal}, pages={848--856}, author={Möller, Heiko and Baier, Moritz and Mecking, Stefan and Talsi, Evgenii P. and Bryliakov, Konstantin P.} }

Mecking, Stefan Bryliakov, Konstantin P. First publ. in: Chemistry : a European journal ; 18 (2012), 3. - S. 848-856 2012-03-20T20:26:22Z 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<sub>3</sub>/CPh<sub>3</sub>B(C<sub>6</sub>F<sub>5</sub>)<sub>4</sub> as activators. Formation of ion pairs of the type [TiL<sub>2</sub>Me][MeMAO] and [TiL<sub>2</sub>Me][B(C<sub>6</sub>F<sub>5</sub>)<sub>4</sub>] has been observed for both catalysts. These ion pairs react with ethene to afford the chain-propagating species [TiL<sub>2</sub>P][MeMAO] and [TiL<sub>2</sub>P][B(C<sub>6</sub>F<sub>5</sub>)<sub>4</sub>], 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<sub>3</sub> and β-hydrogen transfer processes. Möller, Heiko Baier, Moritz deposit-license eng Talsi, Evgenii P. 2012-03-20T20:26:22Z Baier, Moritz Talsi, Evgenii P. Mecking, Stefan Bryliakov, Konstantin P. The origin of living polymerization with an o-fluorinated catalyst : NMR spectroscopic characterization of chain-carrying species Möller, Heiko 2012-01-16

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