A Heterogeneous Palladium Catalyst for the Polymerization of Olefins Prepared by Halide Abstraction Using Surface R3Si+ Species

Date
2022-03-02
Authors
Rossini, Aaron
Dorn, Rick W.
Laurent, Guillaume P.
Perras, Frédéric A.
Rossini, Aaron J.
Conley, Matthew
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Wiley-VCH GmbH
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Ames Laboratory
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Chemistry
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Ames LaboratoryChemistry
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 1shows 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 show that the (N^N)Pd–CH3+ fragment is weakly coordinated to the [(RFO)3Al–OSi≡)] anion, indicating that the palladium fragment interacts with a siloxane bridge on silica. 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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This is the peer-reviewed version of the following article: Gao, Jiaxin, Rick W. Dorn, Guillaume P. Laurent, Frédéric A. Perras, Aaron J. Rossini, and Matthew Conley. "A Heterogeneous Palladium Catalyst for the Polymerization of Olefins Prepared by Halide Abstraction Using Surface R3Si+ Species." Angewandte Chemie (2022), which has been published in final form at DOI: 10.1002/ange.202117279. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Self-Archiving. Copyright 2022 Wiley-VCH GmbH, Weinheim. Posted with permission.
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Palladium, Olefin Polymerization, Polar Monomer, Heterogeneous Catalysis, Solid-state NMR
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