Ethylene Polymerization and Copolymerization with Polar Monomers by Cationic Phosphine Phosphonic Amide Palladium Complexes

Sui, Xuelin; Dai, Shengyu; Chen, Changle

doi:10.1021/acscatal.5b01490

Cited by 129 publications

(88 citation statements)

References 61 publications

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“…This account mainly focuses on phosphinesulfonate ligands for palladium-catalyzed coordinationinsertion copolymerization of olefins and polymer monomers. Other researchers as well as we have devoted their/ our efforts to develop other ligand platforms, representative examples including bisphosphine monoxide (BPMO), 77,78 phosphinephosphinic diamide, 79 phosphinephosphonic amide, 80 IzQO, 72 and carbenephosphine oxide. 81 Meanwhile, nickel complexes have received much attention as novel catalysts for coordinationinsertion copolymerization of olefins and polymer monomers because of the cheap and abundant nature of nickel compared with palladium.…”

Section: 7576mentioning

confidence: 99%

Palladium-Catalyzed Homo- and Copolymerization of Polar Monomers: Synthesis of Aliphatic and Aromatic Polymers

Ito

2018

Bulletin of the Chemical Society of Japan

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Transition-metal-catalyzed coordinationinsertion polymerization of olefins is an indispensable tool in polymer synthesis. When polar monomers with polar functional groups are employed, however, the catalysts are often deactivated owing to side reactions such as σ-coordination and β-elimination of the functional group. Nevertheless, recent progress in late transition metal catalysis has enabled the synthesis of many types of functional polymers from polar monomers through coordinationinsertion polymerization methods. This account describes our achievements in the palladium-catalyzed coordinationinsertion (co)polymerization of polar monomers for the syntheses of a variety of functional polymers, ranging from functionalized polyolefins via olefin/polar monomer copolymerization to o-arylene-containing polymers via formal aryne polymerization.

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Section: 7576mentioning

confidence: 99%

Palladium-Catalyzed Homo- and Copolymerization of Polar Monomers: Synthesis of Aliphatic and Aromatic Polymers

Ito

2018

Bulletin of the Chemical Society of Japan

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“…This year, highly active Ni catalysts have been reported . In addition to the two classes of ligands mentioned above, Pd complexes that have either bis(phosphine) monoxide, phosphine–phosphonic amides, or N‐heterocyclic carbenes catalyze the copolymerization of ethylene with polar vinyl monomers…”

Section: Introductionmentioning

confidence: 99%

Palladium‐Catalyzed Ethylene/Methyl Acrylate Co‐Oligomerization: The Effect of a New Nonsymmetrical α‐Diimine with the 1,4‐Diazabutadiene Skeleton

et al. 2017

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PdII complexes with a nonsymmetrical bis(aryl‐imino)diazabutadiene ligand (ArDAB) have been synthesized and characterized. The new ligand features one aryl ring substituted in the ortho positions with a methyl group and the other ring that bears a trifluoromethyl group on the meta positions, which leads to subtle steric and electronic differences at the two N donor atoms. This peculiar substitution makes the direct synthesis of the ligand unfeasible, and the relevant PdII complex, [Pd(CH3)Cl(ArDAB)], is obtained directly through a template reaction. The corresponding cationic complexes with either acetonitrile or DMSO were synthesized and characterized. The X‐ray crystal structure of a Pd complex with an α‐diimine and DMSO is reported. The monocationic complexes were tested as precatalysts in ethylene/methyl acrylate co‐oligomerization under mild reaction temperature and pressure conditions. A comparison of the catalytic behavior of the precatalysts with the corresponding nonsymmetrical aryl α‐diimines with an acenaphthene skeleton indicated that the active species with the new ligand is more productive and leads to the formation of ethylene oligomers and ethylene/methyl acrylate co‐oligomers.

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“…These cooligomerization parameters are much worse than those of phosphine‐sulfonate palladium catalysts. However, this does represent one of the few catalyst systems that can enable ethylene copolymerizations/cooligomerizations with a series of industrially relevant polar comonomers . The ethylene oligomer generated by Pd‐CH 2 at 20 °C is highly linear based on 13 C NMR analysis (Figure S48, B=3 per 1000 carbon atoms).…”

Section: Resultsmentioning

confidence: 99%

Ethylene (co)Oligomerization by Phosphine‐Pyridine Based Palladium and Nickel Catalysts

Chen

2018

ChemCatChem

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Phosphine and pyridine groups have been widely employed in various olefin polymerization catalysts. In this contribution, these two moieties are connected using different bridges, and the properties of their corresponding palladium and nickel complexes are investigated. A series of CH2, NH and O bridged phosphine‐pyridine ligands (2‐(diarylphosphino)methyl‐pyridine, 2‐(diarylphosphino)amino‐pyridine, 2‐diarylphosphinito‐pyridine) are synthesized and characterized. For the CH2 bridged ligand, the introduction of a C6F5 substituent leads to the generation of a mixture of diastereomers, which can be separated by column chromatography. Starting with these five phosphine‐pyridine ligands, the corresponding palladium and nickel complexes are prepared and characterized. The bridging moiety (CH2, NH and O), the substituents on the bridge, and the ligand orientations significantly influence the properties of the metal complexes in ethylene oligomerization and cooligomerization reactions. For the palladium complexes, ethylene oligomerization and cooligomerization with some polar comonomers (methyl acrylate, butyl vinyl ether, vinyltrimethoxysilane, allyl acetate and allyl choride) can be realized. For the nickel complexes, ethylene oligomerization followed by Friedel‐Crafts addition of the resulting oligomers to toluene solvent leads to the formation of branched alkylated aromatic materials.

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Ethylene Polymerization and Copolymerization with Polar Monomers by Cationic Phosphine Phosphonic Amide Palladium Complexes

Cited by 129 publications

References 61 publications

Palladium-Catalyzed Homo- and Copolymerization of Polar Monomers: Synthesis of Aliphatic and Aromatic Polymers

Palladium-Catalyzed Homo- and Copolymerization of Polar Monomers: Synthesis of Aliphatic and Aromatic Polymers

Palladium‐Catalyzed Ethylene/Methyl Acrylate Co‐Oligomerization: The Effect of a New Nonsymmetrical α‐Diimine with the 1,4‐Diazabutadiene Skeleton

Ethylene (co)Oligomerization by Phosphine‐Pyridine Based Palladium and Nickel Catalysts

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