2,4,6–Triphenylpyridinium: A Bulky, Highly Electron–Withdrawing Substituent Which Enhances Properties of Nickel(II) Ethylene Polymerization Catalysts

Daugulis, Olafs; Brookhart, Maurice; Janeta, Mateusz; Heidlas, Julius X.

doi:10.1002/anie.202013854

2,4,6–Triphenylpyridinium: A Bulky, Highly Electron–Withdrawing Substituent Which Enhances Properties of Nickel(II) Ethylene Polymerization Catalysts

Journal Article · Mon Nov 23 00:00:00 EST 2020 · Angewandte Chemie (International Edition)

DOI:https://doi.org/10.1002/anie.202013854· OSTI ID:1755772

Daugulis, Olafs ^[1]; Brookhart, Maurice ^[2]; Janeta, Mateusz ^[2]; Heidlas, Julius X. ^[2]

Univ. of Houston, TX (United States); University of Houston
Univ. of Houston, TX (United States)

The reactivity of Ni(II) and Pd(II) 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 its’ –CF3 analog. 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 its’ high steric bulk relative to the trifluoromethyl group. This feature results in a four-fold increase in polymer molecular weight due to enhanced retardation of chain transfer. Here, a significant increase in catalyst lifetime is observed as well.

View Accepted Manuscript (DOE)

Research Organization:: Univ. of Houston, TX (United States)

Sponsoring Organization:: USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES); Welch Foundation

Grant/Contract Number:: SC0021403

OSTI ID:: 1755772

Alternate ID(s):: OSTI ID: 1786185

Journal Information:: Angewandte Chemie (International Edition), Journal Name: Angewandte Chemie (International Edition) Journal Issue: 9 Vol. 60; ISSN 1433-7851

Publisher:: WileyCopyright Statement

Country of Publication:: United States

Language:: English

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CCDC 2003990: Experimental Crystal Structure Determination Mateusz, Janeta,; X., Heidlas, Julius; Olafs, Daugulis, https://doi.org/10.5517/ccdc.csd.cc2589vm The current record is supplemented by this dataset	dataset	January 2021
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2,4,6–Triphenylpyridinium: A Bulky, Highly Electron–Withdrawing Substituent Which Enhances Properties of Nickel(II) Ethylene Polymerization Catalysts

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