Succinimide-KI: An efficient binary catalyst system for mild, solvent-free cycloaddition of CO2 to epoxides

Li, Qingshuo; Chang, Haibo; Li, Runming; Wang, Hongxia; Liu, Jichun; Liu, Shanhu; Qiao, Congzhen; Lin, Tong

doi:10.1016/j.mcat.2019.03.012

Cited by 30 publications

(6 citation statements)

References 64 publications

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“…Interestingly, halides such as NaI and KI can be extracted from waste biomass such as seaweed . Nevertheless, group I halides, when used alone, are sluggish catalysts for the target reaction ,− due to poor solubility and low Lewis acidity, and they require the assistance of or activation by additional catalytic components; potassium iodide has been frequently applied as a source of nucleophilic halides in the presence of catalytic components such as amino acids , and other homogeneous ,, or heterogeneous ,− hydrogen bond donors, N-heterocyclic carbenes, , crown ethers, and others . However, the reaction conditions associated with such systems are generally relatively harsh, especially in the case of partially heterogeneous systems where the additional, and often more expensive, catalytic moiety is recovered (80–120 °C, 10–20 bar CO 2 ). ,, This is even more the case of sodium halides as their application in the solventless cycloaddition of CO 2 to epoxides is relatively uncommon and generally requires high reaction temperatures (120–130 °C) and pressures (20–40 bar) − to afford reasonable to high yields of cyclic carbonates.…”

Section: Introductionmentioning

confidence: 99%

Enhancing the Catalytic Performance of Group I, II Metal Halides in the Cycloaddition of CO₂ to Epoxides under Atmospheric Conditions by Cooperation with Homogeneous and Heterogeneous Highly Nucleophilic Aminopyridines: Experimental and Theoretical Study

et al. 2022

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Compared to metal–organic complexes and transition-metal halides, group I metal halides are attractive catalysts for the crucial cycloaddition reaction of CO2 to epoxides as they are ubiquitously available and inexpensive, have a low molecular weight, and are not based on (potentially) endangered metals, especially for the case of sodium and potassium. Nevertheless, given their low intrinsic catalytic efficiency, they require the assistance of additional catalytic moieties. In this work, we show that by exploiting the high nucleophilicity of opportunely designed aminopyridines, catalytic systems based on alkaline metals can be formed, which allow the cycloaddition of CO2 to epoxides to proceed under atmospheric pressure at moderate temperatures. Importantly, the aminopyridine nucleophiles can be applied in their heterogenized form, leading to a recyclable catalytic system. An investigation of the reaction mechanism by density functional theory calculations shows that metal halide complexes and nucleophilic pyridines can work as a dual cooperative catalytic system where the use of aminopyridines leads to lower energy barriers for the opening of the epoxide ring, and halide-adducts are involved in the subsequent steps of CO2 insertion and ring closure.

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Section: Introductionmentioning

confidence: 99%

Enhancing the Catalytic Performance of Group I, II Metal Halides in the Cycloaddition of CO₂ to Epoxides under Atmospheric Conditions by Cooperation with Homogeneous and Heterogeneous Highly Nucleophilic Aminopyridines: Experimental and Theoretical Study

et al. 2022

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“…S8 †). 14 Subsequently, the apparent activation energy and pre-exponential factors can be obtained by using the Arrhenius equation (Fig. 4b).…”

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confidence: 99%

Tubular metal organic frameworks from the curvature of 2D-honeycombed metal coordination

Bao

et al. 2020

Dalton Trans.

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“…The result for ln[PO] ~ t and lnk obs ~ T –1 can be obtained experimentally (Figure ), from which the pre-exponential factor A and the apparent activation energy ( E a ) can be estimated (see the details in Supporting Information), being 2.703 × 10 2 min –1 and 33.30 kJ·mol –1 , respectively. Because the E a for the cycloaddition catalyzed by KI alone was 43.0 kJ·mol –1 , AM and KI lead to activation energy reduction by 9.7 kJ·mol –1 .…”

Section: Resultsmentioning

confidence: 99%

Highly Efficient Solvent-free Conversion of CO₂ into Cyclic Carbonates by Acrylamide–KI

Yang

et al. 2020

Ind. Eng. Chem. Res.

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The cycloaddition of CO2 with epoxide has been a promising way to fix CO2. Developing efficient, low-cost catalysts for this reaction is highly desired. In this paper, we report a novel cocatalyst system that consists of acrylamide and KI for the synthesis of propylene carbonate using CO2 and propylene oxide as starting materials. Different amides (i.e., acrylamide, benzamide, nicotinamide, acetamide, N-isopropylacrylamide, N-tert-butylacrylamide, and N,N-dimethylacrylamide) were combined with different potassium halides to investigate their catalysis capability. KI/acrylamide showed the highest efficiency, and a synergetic effect occurred between acrylamide and KI. At the KI: acrylamide ratio of 1:1 (mol/mol) and concentration of 2.5 mol% for both of them (based on PO), the reaction reached a yield of 95.3%. The catalytic system applies to the cycloaddition reaction using different epoxides. The reaction mechanism was proposed.

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Succinimide-KI: An efficient binary catalyst system for mild, solvent-free cycloaddition of CO2 to epoxides

Cited by 30 publications

References 64 publications

Enhancing the Catalytic Performance of Group I, II Metal Halides in the Cycloaddition of CO₂ to Epoxides under Atmospheric Conditions by Cooperation with Homogeneous and Heterogeneous Highly Nucleophilic Aminopyridines: Experimental and Theoretical Study

Enhancing the Catalytic Performance of Group I, II Metal Halides in the Cycloaddition of CO₂ to Epoxides under Atmospheric Conditions by Cooperation with Homogeneous and Heterogeneous Highly Nucleophilic Aminopyridines: Experimental and Theoretical Study

Tubular metal organic frameworks from the curvature of 2D-honeycombed metal coordination

Highly Efficient Solvent-free Conversion of CO₂ into Cyclic Carbonates by Acrylamide–KI

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Succinimide-KI: An efficient binary catalyst system for mild, solvent-free cycloaddition of CO2 to epoxides

Cited by 30 publications

References 64 publications

Enhancing the Catalytic Performance of Group I, II Metal Halides in the Cycloaddition of CO2 to Epoxides under Atmospheric Conditions by Cooperation with Homogeneous and Heterogeneous Highly Nucleophilic Aminopyridines: Experimental and Theoretical Study

Enhancing the Catalytic Performance of Group I, II Metal Halides in the Cycloaddition of CO2 to Epoxides under Atmospheric Conditions by Cooperation with Homogeneous and Heterogeneous Highly Nucleophilic Aminopyridines: Experimental and Theoretical Study

Tubular metal organic frameworks from the curvature of 2D-honeycombed metal coordination

Highly Efficient Solvent-free Conversion of CO2 into Cyclic Carbonates by Acrylamide–KI

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Enhancing the Catalytic Performance of Group I, II Metal Halides in the Cycloaddition of CO₂ to Epoxides under Atmospheric Conditions by Cooperation with Homogeneous and Heterogeneous Highly Nucleophilic Aminopyridines: Experimental and Theoretical Study

Enhancing the Catalytic Performance of Group I, II Metal Halides in the Cycloaddition of CO₂ to Epoxides under Atmospheric Conditions by Cooperation with Homogeneous and Heterogeneous Highly Nucleophilic Aminopyridines: Experimental and Theoretical Study

Highly Efficient Solvent-free Conversion of CO₂ into Cyclic Carbonates by Acrylamide–KI