Cyclopolymerization and copolymerization of functionalized 1,6-heptadienes catalyzed by Pd complexes: mechanism and application to physical-gel formation

Chemistry : a European Journal
Sehoon ParkKohtaro Osakada

Abstract

Cationic Pd complexes, prepared from [PdCl(ArN=C(12)H(6)=NAr)(Me)] and Na[B{3,5(CF(3))(2)C(6)H(3)}(4)] (NaBARF), catalyze the cyclopolymerization of 4,4-disubstituted 1,6-heptadienes. The polymers produced contain a trans-fused five-membered ring in each repeating unit. NMR spectroscopy and FAB mass spectrometry of the polymers formed indicated that the initiation end of the chain contains either the cyclopentyl group derived from the preformed Pd-monomer complex or a hydrogen atom left on the Pd center by the chain-transfer reaction. The stable cyclopentylpalladium species are involved in both initiation and propagation steps and undergo isomerization into (cyclopentylmethyl)palladium species followed by the insertion of a CH=CH(2) bond of a new monomer molecule into the Pd-CH(2) bond. Copolymerization of 1,6-heptadiene derivatives with ethylene, catalyzed by the Pd complexes, yields polymers that contain trans five-membered rings and branched oligoethylene units. Copolymerization of isopropylidene diallylmalonate with 1-hexene affords a polymer with 26% diene incorporation. The copolymerization consumes 1-hexene more readily than isopropylidene diallylmalonate, although gel permeation chromatography and NMR spectroscopy of th...Continue Reading

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Citations

Feb 14, 2013·Angewandte Chemie·Ian GermanFranck D'Agosto
Dec 6, 2011·Chemistry : a European Journal·Igor L FedushkinGleb A Abakumov
Apr 24, 2018·Journal of the American Chemical Society·David N VaccarelloGeoffrey W Coates

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