Ligand and solvent effects on the catalytic activity and lifetime of zwitterionic Nickel(II) catalysts for alternating CO-Ethylene copolymerization

Zhu, Linhui; Dai, Yiwei; Schrage, Briana R.; Ziegler, Christopher J.; Li, Jia

doi:10.1016/j.jorganchem.2021.122045

Cited by 11 publications

(14 citation statements)

References 39 publications

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“…Compared to PKs obtained with the Pd-PNPO catalyst, the molecular weight distributions produced by Ni complexes were all bimodal (Figures S47-S52 in Supporting Information), which was presumably due to the β-H elimination and further chain transfer reactions initiated by the NiÀ H species. [21,23] In addition, it is observed that the molecular weight has reduced to 998 kg mol À 1 and 805 kg mol À 1 under 0.5 MPa and 1.0 MPa H 2 atmosphere, respectively (Table S4, entries 5 and 6), underlining H 2 can initiate the chain transfer reaction for PNPOÀ Ni catalyzed carbonylative polymerization.…”

Section: Methodsmentioning

confidence: 96%

Cationic P,O‐Coordinated Nickel(II) Catalysts for Carbonylative Polymerization of Ethylene: Unexpected Productivity via Subtle Electronic Variation

Chen

Ren

et al. 2022

Angewandte Chemie

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Transition‐metal‐catalyzed copolymerization of ethylene with carbon monoxide affords polyketones materials with excellent mechanical strength, photodegradability, surface and barrier properties. Unlike the widely used and rather expensive Pd catalysts, Ni‐catalyzed carbonylative polymerization is very difficult since the strong binding affinity of CO to Ni deactivates the highly electrophilic metal center easily. In this study, various cationic P,O‐coordinated Ni complexes were synthesized using the electronic modulation strategy, and the catalyst with strong electron‐donating substituents exhibits an excellent productivity of 104 g polymer (g Ni)−1, which represents a rare discovery that a Ni complex could operate with such exceptional efficiency in comparison with Pd catalysts. Notably, those Ni catalysts were also efficient for terpolymerization of ethylene, propylene with CO for producing commercial polyketone materials with low melting temperatures and easy processibility.

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Section: Methodsmentioning

confidence: 96%

Cationic P,O‐Coordinated Nickel(II) Catalysts for Carbonylative Polymerization of Ethylene: Unexpected Productivity via Subtle Electronic Variation

Chen

Ren

et al. 2022

Angewandte Chemie

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“…The effects of solvent on the synthesis of PK are generally considered to be caused by the polarity or coordination effect of the solvent. [20] In 2021, Zhu et al found that the activity of zwitterionic nickel-based catalyst in THF was several times higher than that in toluene, and proved that the increased activity was attributable to the coordinating ability of THF instead of its polarity. [20] To compare the solvent effects of CH 2 Cl 2 , THF and toluene, Koide and Barron synthesized PK by using dppp-type cationic palladium-based catalysts.…”

Section: Influence Of Solvent Typementioning

confidence: 99%

“…[20] In 2021, Zhu et al found that the activity of zwitterionic nickel-based catalyst in THF was several times higher than that in toluene, and proved that the increased activity was attributable to the coordinating ability of THF instead of its polarity. [20] To compare the solvent effects of CH 2 Cl 2 , THF and toluene, Koide and Barron synthesized PK by using dppp-type cationic palladium-based catalysts. Higher catalytic activity was found in polar solvents.…”

Section: Influence Of Solvent Typementioning

confidence: 99%

“…[ 18 ] Li and co‐workers tried to reduce the deactivation rate by adjusting the ligand of zwitterionic catalysts to improve the productivity. Unfortunately, the highest productivity was only ≈8.4 × 10 3 g PK/g Ni even the reaction time was 90 h. [ 20 ] In 2021, Mecking and co‐workers reported that phosphinophenolato nickel‐based catalysts catalyzed the nonalternating copolymerization of ethylene and CO, incorporating low‐density ketone groups into PE chains. The products possess the desired material properties and photodegradation performance.…”

Section: Introductionmentioning

confidence: 99%

“…[18] Recently, several studies have been focused on zwitterionic nickel-based catalysts for the preparation of PK. [19,20] The activity of zwitterionic catalysts was very high, 15.5 × 10 3 g PK/(g Ni h), in the first 5 min, and decreased quickly later, which resulted in low productivity. [18] Li and co-workers tried to reduce the deactivation rate by adjusting the ligand of zwitterionic catalysts to improve the productivity.…”

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Studies on Alternating Copolymerization of Ethylene and Carbon Monoxide Using Nickel‐Based Catalyst: Cocatalyst and the Polarity of Solvent

Bie

et al. 2021

Macro Reaction Engineering

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Polyketone (PK) has attracted wide attention owing to its direct utilization of carbon monoxide, excellent properties, and photodegradation performance. However, the commercialized PK is produced using Pd‐based catalysts, which accounts for the largest part of the production cost. Herein, [Ni(2‐tol)(PPh3)(N,O)] is used as the main catalyst for its high productivity and good tolerance to CO. Effects of the cocatalyst (Ni(COD)2), the aging method in CO atmosphere, and the polarity of solvent are investigated. When Ni(COD)2 is employed as the cocatalyst, the catalytic activity and molecular weight of PK are increased by 29% and 42.6%, respectively. Aging of catalyst system with Ni(COD)2 in CO atmosphere leads to significant decrease in activity and molecular weight, while aging has almost no effect on the copolymerization without Ni(COD)2. Different catalytic mechanisms are proposed for the catalyst system with and without cocatalyst. Furthermore, it is found that the polar solvent (CH2Cl2) significantly increases the activity by 119.2% compared to that in the nonpolar solvent (toluene). However, the thermal stability of the catalyst is much better in toluene. The study on the understanding of catalytic mechanism and improvement of activity will promote the practical application of nonprecious metal catalysts for preparation of PK.

show abstract

Cationic P,O‐Coordinated Nickel(II) Catalysts for Carbonylative Polymerization of Ethylene: Unexpected Productivity via Subtle Electronic Variation

Chen

Ren

et al. 2022

Angew Chem Int Ed

View full text Add to dashboard Cite

Transition-metal-catalyzed copolymerization of ethylene with carbon monoxide affords polyketones materials with excellent mechanical strength, photodegradability, surface and barrier properties. Unlike the widely used and rather expensive Pd catalysts, Nicatalyzed carbonylative polymerization is very difficult since the strong binding affinity of CO to Ni deactivates the highly electrophilic metal center easily. In this study, various cationic P,O-coordinated Ni complexes were synthesized using the electronic modulation strategy, and the catalyst with strong electron-donating substituents exhibits an excellent productivity of 10 4 g polymer (g Ni) À 1 , which represents a rare discovery that a Ni complex could operate with such exceptional efficiency in comparison with Pd catalysts. Notably, those Ni catalysts were also efficient for terpolymerization of ethylene, propylene with CO for producing commercial polyketone materials with low melting temperatures and easy processibility.

show abstract

Ligand and solvent effects on the catalytic activity and lifetime of zwitterionic Nickel(II) catalysts for alternating CO-Ethylene copolymerization

Cited by 11 publications

References 39 publications

Cationic P,O‐Coordinated Nickel(II) Catalysts for Carbonylative Polymerization of Ethylene: Unexpected Productivity via Subtle Electronic Variation

Cationic P,O‐Coordinated Nickel(II) Catalysts for Carbonylative Polymerization of Ethylene: Unexpected Productivity via Subtle Electronic Variation

Studies on Alternating Copolymerization of Ethylene and Carbon Monoxide Using Nickel‐Based Catalyst: Cocatalyst and the Polarity of Solvent

Cationic P,O‐Coordinated Nickel(II) Catalysts for Carbonylative Polymerization of Ethylene: Unexpected Productivity via Subtle Electronic Variation

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