The Origin of Living Polymerization with an o-Fluorinated Catalyst: NMR-Spectroscopic Characterization of Chain-Carrying Species Full article
| Journal |
Chemistry - A European Journal
ISSN: 0947-6539 , E-ISSN: 1521-3765 |
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| Output data | Year: 2012, Volume: 18, Pages: 848-856 Pages count : 9 DOI: 10.1002/chem.201102408 | ||||
| Tags | fluorine, ion pairs, living polymerization, reaction mechanisms, titanium | ||||
| Authors |
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| Affiliations |
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Funding (2)
| 1 | Russian Foundation for Basic Research | 10-03-91330 |
| 2 | German Research Foundation | Me 1388/9-1 |
Abstract:
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 b-hydrogen transfer processes.
Cite:
Möller H.M.
, Baier M.C.
, Mecking S.
, Talsi E.P.
, Bryliakov K.P.
The Origin of Living Polymerization with an o-Fluorinated Catalyst: NMR-Spectroscopic Characterization of Chain-Carrying Species
Chemistry - A European Journal. 2012. V.18. P.848-856. DOI: 10.1002/chem.201102408 WOS Scopus РИНЦ ANCAN PMID OpenAlex
The Origin of Living Polymerization with an o-Fluorinated Catalyst: NMR-Spectroscopic Characterization of Chain-Carrying Species
Chemistry - A European Journal. 2012. V.18. P.848-856. DOI: 10.1002/chem.201102408 WOS Scopus РИНЦ ANCAN PMID OpenAlex
Dates:
| Submitted: | Aug 3, 2011 |
| Published online: | Dec 13, 2011 |
| Published print: | Jan 16, 2012 |
Identifiers:
| Web of science: | WOS:000298919400017 |
| Scopus: | 2-s2.0-84855657115 |
| Elibrary: | 17973818 |
| Chemical Abstracts: | 2011:1609888 |
| Chemical Abstracts (print): | 156:560930 |
| PMID: | 22170534 |
| OpenAlex: | W2044802626 |