2,4,6-Triphenylpyridinium: A Bulky, Highly Electron-Withdrawing Substituent That Enhances Properties of Nickel(II) Ethylene Polymerization Catalysts
Dr. Mateusz Janeta
Department of Chemistry, University of Houston, Houston, TX, 77204-5003 USA
Faculty of Chemistry, University of Wrocław, F. Joliot-Curie 14, 50-383 Wrocław, Poland
Search for more papers by this authorJulius X. Heidlas
Department of Chemistry, University of Houston, Houston, TX, 77204-5003 USA
Search for more papers by this authorCorresponding Author
Prof. Dr. Olafs Daugulis
Department of Chemistry, University of Houston, Houston, TX, 77204-5003 USA
Search for more papers by this authorCorresponding Author
Prof. Dr. Maurice Brookhart
Department of Chemistry, University of Houston, Houston, TX, 77204-5003 USA
Search for more papers by this authorDr. Mateusz Janeta
Department of Chemistry, University of Houston, Houston, TX, 77204-5003 USA
Faculty of Chemistry, University of Wrocław, F. Joliot-Curie 14, 50-383 Wrocław, Poland
Search for more papers by this authorJulius X. Heidlas
Department of Chemistry, University of Houston, Houston, TX, 77204-5003 USA
Search for more papers by this authorCorresponding Author
Prof. Dr. Olafs Daugulis
Department of Chemistry, University of Houston, Houston, TX, 77204-5003 USA
Search for more papers by this authorCorresponding Author
Prof. Dr. Maurice Brookhart
Department of Chemistry, University of Houston, Houston, TX, 77204-5003 USA
Search for more papers by this authorAbstract
The reactivity of NiII and PdII olefin polymerization catalysts can be enhanced by introduction of electron-withdrawing substituents on the supporting ligands rendering the metal centers more electrophilic. Reported here is a comparison of ethylene polymerization activity of a classical salicyliminato nickel catalyst substituted with the powerful electron-withdrawing 2,4,6-triphenylpyridinium (trippy) group to the -CF3 analogue. The trippy substituent is substantially more electron-withdrawing (σmeta=0.63) than the trifluoromethyl group (σmeta=0.43) which results in a ca. 8-fold increase in catalytic turnover frequency. An additional advantage of trippy is the high steric bulk relative to the trifluoromethyl group. This feature results in a four-fold increase in polymer molecular weight owing to enhanced retardation of chain transfer. A significant increase in catalyst lifetime is observed as well.
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