Repetitive Ethylene Insertion into the Pd-OAc Bond: Synthesis of Heterotelechelic Polyethylene and Effective Copolymerization of Ethylene with Vinyl or Allyl Acetate
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Updated: Jun 25, 2026

Ethylene Polymerizations Using Parallel Pressure Reactors and a Kinetic Analysis of Chain Transfer Polymerization
Published on: November 27, 2015
Yusuke Hori1, Rin Seki1, Ryo Mandai1
1Department of Chemistry and Biotechnology, Graduate School of Engineering, The University of Tokyo, Bunkyo-ku, Tokyo 113-8656, Japan.
Abstract:
Palladium-catalyzed oxidative functionalization of ethylene, exemplified by Wacker oxidation, has been fundamental in organic chemistry. Despite the potentially versatile reactivity of Pd-alkyl intermediates formed after oxypalladation of ethylene, explorations of their subsequent reactions are limited due to the rapid β-H elimination. Here we found that the palladium acetate complex bearing a phosphine-sulfonate ligand containing a 2,5-dichlorothiophene-3,4-diyl backbone enables multiple ethylene insertion into the Pd-OAc bond by suppressing the competing β-H elimination. This reactivity provides access to heterotelechelic polyethylene and facilitates the copolymerization of ethylene with vinyl acetate or allyl acetate.
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