Facile synthesis of sterically demanding SHOP‐type nickel catalysts for ethylene polymerization

Peng, Dan; Pang, Wenmin; Xu, Guoyong; Tan, Chen; Wang, Fuzhou

doi:10.1002/aoc.5054

Cited by 19 publications

(10 citation statements)

References 77 publications

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“…Metal catalysis can help to streamline and ease the initiation and continuation of the polymerization. Nickel has been a predominate polymerization catalyst in many reactions both heterogeneously, , and homogeneously in the form of α-diimino complexes. − With bidentate phosphines, the most extensive use has been to synthesize precursors for Kumada catalyst-transfer polymerization (KCTP) reactions. Some of these reactions use only (dppe)NiCl 2 or (dppp)NiCl 2 for the polymerization and so are not covered in our study. − …”

Section: Polymerizationmentioning

confidence: 99%

Trends in the Usage of Bidentate Phosphines as Ligands in Nickel Catalysis

et al. 2020

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A critically important process in catalysis is the formation of an active catalyst from the combination of a metal precursor and a ligand, as the efficacy of this reaction governs the amount of active catalyst. This Review is a comprehensive overview of reactions catalyzed by nickel and an added bidentate phosphine, focusing on the steps transforming the combination of precatalyst and ligand into an active catalyst and the potential effects of this transformation on nickel catalysis. Reactions covered include common cross-coupling reactions, such as Suzuki, Heck, Kumada, and Negishi couplings, addition reactions, cycloadditions, C−H functionalizations, polymerizations, hydrogenations, and reductive couplings, among others. Overall, the most widely used nickel precatalyst with free bidentate phosphines is Ni(cod) 2 , which accounts for ∼50% of the reports surveyed, distantly followed by Ni(acac) 2 and Ni(OAc) 2 , which account for ∼10% each. By compiling the reports of these reactions, we have calculated statistics of the usage and efficacy of each ligand with Ni(cod) 2 and other nickel sources. The most common bidentate phosphines are simple, relatively inexpensive ligands, such as DPPE, DCPE, DPPP, and DPPB, along with others with more complex backbones, such as DPPF and Xantphos. The use of expensive chiral phosphines is more scattered, but the most common ligands include BINAP, Me-Duphos, Josiphos, and related analogs.

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Section: Polymerizationmentioning

confidence: 99%

Trends in the Usage of Bidentate Phosphines as Ligands in Nickel Catalysis

et al. 2020

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“…[7] As for the use of phosphines as ancillary ligands of catalysts based on late transition metals for ethylene oligomerization and homopolymerization, some remarkable examples of Ni(II) complexes have been reported. In addition to the bulky phosphino-based SHOP catalysts [8] and the bulky iminophosphine-Ni complexes, [9] they also include catalysts based on either bidentate [10] or monodentate phosphines. [11] On the other hand, to the best of our knowledge only a few examples of the use of Pd(II) can be found.…”

Section: Introductionmentioning

confidence: 99%

Palladium(II) Complexes with the 4,5‐Bis(diphenylphosphino)acenaphthene Ligand and Their Reactivity with Ethylene

et al. 2022

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The last two decades have witnessed the development of homogeneous catalysts for ethylene homo‐ and co‐polymerization reactions based on late transition metals. When Pd(II) is the metal of choice, the best ligand‐metal combination deals with either bidentate nitrogen‐donor molecules or phosphinobenzene sulfonate derivatives. In this contribution we have investigated the coordination chemistry to Pd(II) of a bidentate phosphorus ligand, namely 4,5‐bis(diphenylphosphino)acenaphthene (1). Starting from the neutral complex, [Pd(1)(CH3)Cl], we obtained the cationic derivatives [Pd(1)(CH3)(L)][SbF6], with L being either CH3CN or 3,5‐lutidine. Using in situ NMR spectroscopy we investigated the reaction of [Pd(1)(CH3)(NCCH3)][SbF6] with ethylene, at room temperature, and ambient ethylene pressure. We discovered that [Pd(1)(CH3)(NCCH3)][SbF6] acts as a catalyst for butenes and hexenes synthesis with the relevant Pd‐ethyl intermediate as the catalyst resting state. At the same time the color of the solution turned from pale yellow to light red due to the formation of the dinuclear species [Pd(μ‐η2−C6H5)PPh)−PPh2]2[SbF6]2. Both the neutral Pd(II) complex, activated in situ by NaSbF6, and the monocationic acetonitrile derivative were tested in the ethylene homopolymerization reaction at high pressure, leading to low molecular weight, branched, polyethylene.

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“…Mononuclear nickel and palladium catalysts were used in this type of polymerization and showed diverse catalytic activity against polar monomers [5,11–16] . Mostly, these structures were based on α‐diimine ligands used for copolymerization of α‐olefin with polar monomers [17–23] .…”

Section: Introductionmentioning

confidence: 99%

Microstructural, Thermal and Electrical Properties of Methyl Methacrylate and 1‐Hexene Copolymers Made by Dinuclear Ni‐Based Catalysts

2021

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Herein, we investigate the dinuclearity effect of α‐diimine Ni‐based catalysts, N1 and N2 bearing different backbone on methyl methacrylate/1‐hexene (MM‐1H) copolymerization and characterize the copolymers microstructures using FT‐IR and NMR. The monomer reactivity ratio (r) is calculated using three different methods, a high reactivity ratio for MM (r1=9.9611), whereas a low reactivity ratio is obtained for 1H (r2=−0.0226). As determined by NMR analyses, up to 96 % of the MM incorporated into the main chain. Thermal copolymer properties are studied by DSC and TGA analyses, and the results are compared with those of Poly (methyl methacrylate) (PMMA). The higher content of MM in the copolymer backbone and the higher Tg for the copolymer samples (95.5 to 105.6 °C) were obtained. TGA shows that the degradation temperature of copolymers with higher 1H content progression reduced by about 10 % weight‐loss for N1 (327 to 240 °C) and N2 (325 to 236 °C). We are using a novel method with a low‐cost and speedy determination of polymer conductivity in both solid and liquid phases, which indicates the semi‐conductivity property of poly(MM‐1H) using corona discharges under the air atmosphere. Synthesized graphene‐poly(MM‐1H) nanocomposite shows the electrical conductivity augment from 3.45 μS of the poly(MM‐1H) to 30.42 μS for its nanocomposite.

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Facile synthesis of sterically demanding SHOP‐type nickel catalysts for ethylene polymerization

Cited by 19 publications

References 77 publications

Trends in the Usage of Bidentate Phosphines as Ligands in Nickel Catalysis

Trends in the Usage of Bidentate Phosphines as Ligands in Nickel Catalysis

Palladium(II) Complexes with the 4,5‐Bis(diphenylphosphino)acenaphthene Ligand and Their Reactivity with Ethylene

Microstructural, Thermal and Electrical Properties of Methyl Methacrylate and 1‐Hexene Copolymers Made by Dinuclear Ni‐Based Catalysts

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