A Heterogeneous Palladium Catalyst for the Polymerization of Olefins Prepared by Halide Abstraction Using Surface R 3 Si + Species - Sorbonne Université Access content directly
Journal Articles Angewandte Chemie International Edition Year : 2022

A Heterogeneous Palladium Catalyst for the Polymerization of Olefins Prepared by Halide Abstraction Using Surface R 3 Si + Species

Abstract

The silylium-like surface species [iPr3Si][(RFO)3Al−OSi≡)] activates (N^N)Pd(CH3)Cl (N^N=Ar−N=CMeMeC=N−Ar, Ar=2,6-bis(diphenylmethyl)-4-methylbenzene) by chloride ion abstraction to form [(N^N)Pd−CH3][(RFO)3Al−OSi≡)] (1). A combination of FTIR, solid-state NMR spectroscopy, and reactions with CO or vinyl chloride establish that 1 shows similar reactivity patterns as (N^N)Pd(CH3)Cl activated with Na[B(ArF)4]. Multinuclear 13C{27Al} RESPDOR and 1H{19F} S-REDOR experiments are consistent with a weakly coordinated ion-pair between (N^N)Pd−CH3+ and [(RFO)3Al−OSi≡)]. 1 catalyzes the polymerization of ethylene with similar activities as [(N^N)Pd−CH3]+ in solution and incorporates up to 0.4 % methyl acrylate in copolymerization reactions. 1 produces polymers with significantly higher molecular weight than the solution catalyst, and generates the highest molecular weight polymers currently reported in copolymerization reactions of ethylene and methylacrylate.
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Origin : Files produced by the author(s)
Origin : Files produced by the author(s)

Dates and versions

hal-03905712 , version 1 (12-05-2023)

Identifiers

Cite

Jiaxin Gao, Rick Dorn, Guillaume P. Laurent, Frédéric Perras, Aaron Rossini, et al.. A Heterogeneous Palladium Catalyst for the Polymerization of Olefins Prepared by Halide Abstraction Using Surface R 3 Si + Species. Angewandte Chemie International Edition, 2022, 61 (20), pp.e202117279. ⟨10.1002/anie.202117279⟩. ⟨hal-03905712⟩
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