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Remote Perfluoroalkyl Substituents are Key to Living Aqueous Ethylene Polymerization.

ABSTRACT: In various nickel(II) salicylaldiminato ethylene polymerization catalysts, which are a versatile mechanistic probe for substituent effects, longer perfluoroalkyl groups exert a strong effect on catalytic activities and polymer microstructures compared to the trifluoromethyl group. This effect is accounted for by a reduced electron density on the active sites, and is also supported by electrochemical studies. Thus, ?-hydride elimination, the key step of chain transfer and branching pathways, is disfavored while chain-growth rates are enhanced. This enhancement occurs to an extent that enables living polymerizations in aqueous systems to afford ultra-high-molecular-weight polyethylene for various chelating salicylaldimine motifs. These findings are mechanistically instructive as well as practically useful for illustrating the potential of perfluoroalkyl groups in catalyst design.

SUBMITTER: Schnitte M

PROVIDER: S-EPMC7027523 | biostudies-literature | 2020 Feb

REPOSITORIES: biostudies-literature

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Remote Perfluoroalkyl Substituents are Key to Living Aqueous Ethylene Polymerization.

Schnitte Manuel M Scholliers Janine S JS Riedmiller Kai K Mecking Stefan S

Angewandte Chemie (International ed. in English) 20200121 8

In various nickel(II) salicylaldiminato ethylene polymerization catalysts, which are a versatile mechanistic probe for substituent effects, longer perfluoroalkyl groups exert a strong effect on catalytic activities and polymer microstructures compared to the trifluoromethyl group. This effect is accounted for by a reduced electron density on the active sites, and is also supported by electrochemical studies. Thus, β-hydride elimination, the key step of chain transfer and branching pathways, is d ...[more]

PMID: 31773825

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