Publikation: Polymer Microstructure Control in Catalytic Polymerization Exclusively by Electronic Effects of Remote Substituents
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2007
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Advanced Synthesis and Catalysis. 2007, 349(14/15), pp. 2307-2316. ISSN 1615-4150. eISSN 1615-4169. Available under: doi: 10.1002/adsc.200700127
Zusammenfassung
A series of (2-N,O)salicylaldiminato nickel methyl pyridine complexes 8a-h-pyr bearing 2,6-di-(4-R-phenyl)phenyl groups on the imine nitrogen and varying in the remote substituents [R=C8F17 (a), CF3 (b), F (7c), H (d), Me (e), tert.-butyl (f), OMe (g), and NMe2 (h)] were studied as precatalysts for ethylene polymerization. Complexes 8a-h-pyr catalyze the polymerization of ethylene to low molecular weight polyethylene. Decreasing molecular weight and increasing degrees of branching are observed in the order R=C8F17CF3>F>H>Me>MeO>tert-butyl>NMe2. X-Ray diffraction analysis of complex 8c-pyr and polymerization results obtained with complexes 8-pyr indicate that it is not the sterics but the electronics of the R group that control the polymer microstructure. This is a rare example of a polymerization catalyst in which substituents effects can clearly be traced to electronics exclusively.
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540 Chemie
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catalyst design, electronic structure, nickel, polymerization
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BASTERO, Amaia, Inigo GÖTTKER-SCHNETMANN, Caroline RÖHR, Stefan MECKING, 2007. Polymer Microstructure Control in Catalytic Polymerization Exclusively by Electronic Effects of Remote Substituents. In: Advanced Synthesis and Catalysis. 2007, 349(14/15), pp. 2307-2316. ISSN 1615-4150. eISSN 1615-4169. Available under: doi: 10.1002/adsc.200700127BibTex
@article{Bastero2007Polym-9857,
year={2007},
doi={10.1002/adsc.200700127},
title={Polymer Microstructure Control in Catalytic Polymerization Exclusively by Electronic Effects of Remote Substituents},
number={14/15},
volume={349},
issn={1615-4150},
journal={Advanced Synthesis and Catalysis},
pages={2307--2316},
author={Bastero, Amaia and Göttker-Schnetmann, Inigo and Röhr, Caroline and Mecking, Stefan}
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<dcterms:abstract xml:lang="eng">A series of (2-N,O)salicylaldiminato nickel methyl pyridine complexes 8a-h-pyr bearing 2,6-di-(4-R-phenyl)phenyl groups on the imine nitrogen and varying in the remote substituents [R=C8F17 (a), CF3 (b), F (7c), H (d), Me (e), tert.-butyl (f), OMe (g), and NMe2 (h)] were studied as precatalysts for ethylene polymerization. Complexes 8a-h-pyr catalyze the polymerization of ethylene to low molecular weight polyethylene. Decreasing molecular weight and increasing degrees of branching are observed in the order R=C8F17CF3>F>H>Me>MeO>tert-butyl>NMe2. X-Ray diffraction analysis of complex 8c-pyr and polymerization results obtained with complexes 8-pyr indicate that it is not the sterics but the electronics of the R group that control the polymer microstructure. This is a rare example of a polymerization catalyst in which substituents effects can clearly be traced to electronics exclusively.</dcterms:abstract>
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