Coupling reaction of carbon dioxide and epoxides efficiently catalyzed by one-component aluminum–salen complex under solvent-free conditions

Tian, Dawei; Liu, Binyuan; Zhang, Li; Wang, Xiaoyang; Zhang, Wei; Han, Lina; Park, Dae‐Won

doi:10.1016/j.jiec.2012.01.034

Cited by 35 publications

(3 citation statements)

References 56 publications

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“…However, to date, only a few industrial processes utilize CO 2 as raw material, because CO 2 is the most oxidized state of carbon, and it has inherent thermodynamic stability and kinetic inertness. 2 In past decades, a plethora of catalytic systems for producing cyclic carbonates have been successfully developed, including alkali metal salts, 3 metal oxides, 4 quaternary ammonium salts, 5 Schiff base, 6 transition metal complex, 7 ion-exchange resins, 8 and active species supported on natural or synthesized polymers, 9 silica, 10 zeolite, 11 and other materials. 12 However, the homogeneous catalysts have problems such as rigorous separation and purification of the products, and the heterogeneous systems are restricted due to the formation of side products as well as harsh reaction conditions, cosolvent requirement, and expensive catalyst.…”

Section: Introductionmentioning

confidence: 99%

Kinetics and Mechanistic Insight into Efficient Fixation of CO₂ to Epoxides over N-Heterocyclic Compound/ZnBr₂ Catalysts

Liu

Zhong

et al. 2015

Ind. Eng. Chem. Res.

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In this contribution, a series of N-heterocyclic compounds cooperated with ZnBr 2 catalyst for chemical fixation of CO 2 to cyclic carbonates was developed without utilization of additional organic solvents. It was found that the catalytic activity of N-heterocyclic compounds could be obviously enhanced in the presence of ZnBr 2 , and the N-methylimidazole (Mim)/ZnBr 2 catalytic system was the most efficient among the catalysts employed. Under the optimum reaction conditions, 99% yield of propylene carbonate was achieved with TOF of 474 h −1 , and the catalysts were also versatile for CO 2 cycloaddition with less active epoxides such as styrene oxide and cyclohexene oxide. Furthermore, a possible synergistic catalytic mechanism was proposed. Moreover, the rate constants were determined as a function of reaction temperature in the range of 130−160 °C, the activation energy was determined to be 41.1 kJ•mol −1 , and the kinetic equation on the synthesis of propylene carbonate catalyzed by Mim/ZnBr 2 was also obtained.

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Section: Introductionmentioning

confidence: 99%

Kinetics and Mechanistic Insight into Efficient Fixation of CO₂ to Epoxides over N-Heterocyclic Compound/ZnBr₂ Catalysts

Liu

Zhong

et al. 2015

Ind. Eng. Chem. Res.

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“…Moreover, complex 2 /TBAB all showed well catalytic performance, the TOF value reached 348 h − 1 . Liu et al [34] reproted aluminum (salen) complexes as catalyst for the synthesis of propylene carbonate, and the TOF was as low as 189 h − 1 . The chromium-salen complexes of Ramin et al [35] showed propylene carbonate TOF of 90–330 h − 1 at 140 °C.…”

Section: Resultsmentioning

confidence: 99%

New Coordination Complexes Based on the 2,6-bis[1-(Phenylimino)ethyl] Pyridine Ligand: Effective Catalysts for the Synthesis of Propylene Carbonates from Carbon Dioxide and Epoxides

Wang

Liu

et al. 2018

Molecules

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We aimed to develop new effective catalysts for the synthesis of propylene carbonate from propylene oxide and carbon dioxide. A kind of Mx+LClx coordination complex was fabricated based on the chelating tridentate ligand 2,6-bis[1-(phenylimino)ethyl] pyridine (L). The obtained products were characterized by elemental analysis, infrared spectroscopy, ultraviolet spectroscopy, thermogravimetric analysis, and single-crystal X-ray diffraction. It was found that the catalytic activity of the complexes with different metal ions, the same ligand differed and co-catalyst, where the order of greatest to least catalytic activity was 2 > 3 > 1. The catalytic system composed of complex 2 and DMAP proved to have the better catalytic performance. The yields for complex 2 systems was 86.7% under the reaction conditions of 100 °C, 2.5 MPa, and 4 h. The TOF was 1026 h−1 under the reaction conditions of 200 °C, 2.5 MPa, and 1 h. We also explored the influence of time, pressure, temperature, and reaction substrate concentration on the catalytic reactions. A hypothetical catalytic reaction mechanism is proposed based on density functional theory (DFT) calculations and the catalytic reaction results.

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“…In addition to binary catalytic system, there is a tendency to employ a bifunctional catalyst in which nucleophile and Lewis metal complexes are constructed into one molecule as the one-component catalyst for the coupling of CO 2 with epoxides in the past decade [58][59][60][61][62][63][64][65][66][67][68]. Quaternary ammonium halide as a nucleophile is usually integrated into the metal complex to construct an ionic bifunctional catalyst.…”

Section: Introductionmentioning

confidence: 99%

Syntheses, Characterization, and Application of Tridentate Phenoxyimino-Phenoxy Aluminum Complexes for the Coupling of Terminal Epoxide with CO2: From Binary System to Single Component Catalyst

Zhang

Wang

Xiang³

et al. 2021

Catalysts

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A series of binuclear aluminum complexes 1–3 supported by tridentate phenoxyimino-phenoxy ligands was synthesized and used as catalysts for the coupling reaction of terminal epoxide with carbon dioxide. The aluminum complex 1, which is catalytically inactive toward the coupling of epoxide with CO2 by itself, shows moderate activity in the presence of excess nucleophiles or organic bases at high temperature. In sharp contrast to complex 1, bifunctional complexes 2 and 3, which incorporate tertiary amine groups as the built-in nucleophile, are able to efficiently transform terminal epoxide with CO2 to corresponding cyclic carbonates as a sole product by themselves at 100 °C. The number of amine groups on the ligand skeleton and the reaction temperature exert a great influence on the catalytic activity. The bifunctional complexes 2 and 3 are also active at low carbon dioxide pressure such as 2 atm or atmospheric CO2 pressure. Kinetic studies of the coupling reactions of chloropropylene oxide/CO2 and styrene oxide/CO2 using bifunctional catalysts under atmospheric pressure of CO2 demonstrate that the coupling reaction has a first-order dependence on the concentration of the epoxide.

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Coupling reaction of carbon dioxide and epoxides efficiently catalyzed by one-component aluminum–salen complex under solvent-free conditions

Cited by 35 publications

References 56 publications

Kinetics and Mechanistic Insight into Efficient Fixation of CO₂ to Epoxides over N-Heterocyclic Compound/ZnBr₂ Catalysts

Kinetics and Mechanistic Insight into Efficient Fixation of CO₂ to Epoxides over N-Heterocyclic Compound/ZnBr₂ Catalysts

New Coordination Complexes Based on the 2,6-bis[1-(Phenylimino)ethyl] Pyridine Ligand: Effective Catalysts for the Synthesis of Propylene Carbonates from Carbon Dioxide and Epoxides

Syntheses, Characterization, and Application of Tridentate Phenoxyimino-Phenoxy Aluminum Complexes for the Coupling of Terminal Epoxide with CO2: From Binary System to Single Component Catalyst

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Coupling reaction of carbon dioxide and epoxides efficiently catalyzed by one-component aluminum–salen complex under solvent-free conditions

Cited by 35 publications

References 56 publications

Kinetics and Mechanistic Insight into Efficient Fixation of CO2 to Epoxides over N-Heterocyclic Compound/ZnBr2 Catalysts

Kinetics and Mechanistic Insight into Efficient Fixation of CO2 to Epoxides over N-Heterocyclic Compound/ZnBr2 Catalysts

New Coordination Complexes Based on the 2,6-bis[1-(Phenylimino)ethyl] Pyridine Ligand: Effective Catalysts for the Synthesis of Propylene Carbonates from Carbon Dioxide and Epoxides

Syntheses, Characterization, and Application of Tridentate Phenoxyimino-Phenoxy Aluminum Complexes for the Coupling of Terminal Epoxide with CO2: From Binary System to Single Component Catalyst

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Kinetics and Mechanistic Insight into Efficient Fixation of CO₂ to Epoxides over N-Heterocyclic Compound/ZnBr₂ Catalysts

Kinetics and Mechanistic Insight into Efficient Fixation of CO₂ to Epoxides over N-Heterocyclic Compound/ZnBr₂ Catalysts