Highly active dinuclear cobalt complexes for solvent-free cycloaddition of CO<sub>2</sub> to epoxides at ambient pressure

Younus, Hussein A.; Ahmad, Najid; Ullah, Habib; Suleman, Suleman; Hossain, Md. Shahadat; Elkadi, Mirella; Verpoort, Francis

doi:10.1039/c9cc02626f

Cited by 43 publications

(19 citation statements)

References 46 publications

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“…This is the first example of amino-bridged bis(phenolato) cobalt complexes capable of catalyzing the cycloaddition reaction under ambient pressure, as reported examples required a pressure of 10–40 bar, regardless of whether they are Co(II) or Co(III) complexes. , Compared with Co(II) and Co(III) Schiff base complexes that are highly active under ambient pressure at 120 °C developed by Verpoort et al, , complexes 2 and 5 worked at a lower temperature of 65 °C.…”

Section: Resultsmentioning

confidence: 79%

Synthesis, Characterization, and Catalytic Study of Amine-Bridged Bis(phenolato) Co(II) and Co(II/III)-M(I) Complexes (M = K or Na)

Wang

Yuan

et al. 2021

Inorg. Chem.

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Co(II) complexes 1−3 bearing amine-bridged bis(phenolato) complexes have been synthesized through reactions of bis(phenols) with CoCl 2 or Co(OAc) 2 . Oxidation of the Co(II) complex with air resulted in partial oxidation, generating mixed valence Co(II/III) complexes 4 and 5. In addition, due to the presence of alkali compounds (KOAc and NaOMe), 4 and 5 formed as Co-alkali metal heterometallic complexes, which are the first example of mixed valence Co(II/III)-M(I) (M = K or Na) complexes. Complexes 1−5 showed good activity in the cycloaddition of epoxides and CO 2 under atmospheric pressure, generating cyclic carbonates in 40−99% yields. Co(II/III)-Na(I) complex 5 performed better in reactions of bulkier substrates, underlining the enhanced activity of mixed valence Co-alkali metal heterometallic complexes. On the contrary, complex 5 showed limited activity in copolymerization of epoxide and CO 2 .

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Section: Resultsmentioning

confidence: 79%

Synthesis, Characterization, and Catalytic Study of Amine-Bridged Bis(phenolato) Co(II) and Co(II/III)-M(I) Complexes (M = K or Na)

Wang

Yuan

et al. 2021

Inorg. Chem.

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“…At the same S/C ratio, the yields for Al-HIP and Zn-HIP are 66 and 72%, respectively. M-HIPs exhibit better activities under ambient conditions compared to previous metallosalen-based catalysts, which usually function under harsh conditions and/or in the presence of nucleophiles. − The ratio of ionic/metal units is crucial to the CO 2 cycloaddition of epoxides according to the previous literature . However, M-HIPs in this work have nearly the same ratios of ionic/metal active sites (Table S2), and the difference in activity is due to the different metal active sites.…”

Section: Resultsmentioning

confidence: 52%

Porous Metallosalen Hypercrosslinked Ionic Polymers for Cooperative CO₂ Cycloaddition Conversion

Han

et al. 2019

Ind. Eng. Chem. Res.

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Metallosalen-based porous ionic polymers have the potential to combine the merits of homogeneous organometallics and heterogeneous porous ionic catalysts in carbon dioxide (CO2) cycloaddition conversion. Herein, a series of porous metallosalen hypercrosslinked ionic polymers (M-HIPs) were synthesized through a simple method. The M-HIPs with high metal and Br anion concentrations were evaluated by catalyzing CO2 cycloaddition with epoxides. Because of the cooperative effect between Br anions and metal active species in the porous channel, M-HIPs exhibited a high CO2 catalytic performance even under ambient conditions. Among the M-HIPs (M = Co, Al, Zn), Co-HIP showed the best catalytic performance for various epoxides and was stable after five runs. Density functional theory calculations support the fact that Co-HIP had the lowest energy barrier, which agreed with the experimental results.

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“…Various epoxides (even the inert aliphatic long-chain epoxides) give high yields within 24 h under the optimal conditions of 10 mmol of epoxide, 0.1 g of catalyst, 303 K, and 1 bar (Figure ). Previously, the results relative to the Co-based catalysts for the CO 2 cycloaddition of epoxide still relied on adding co-catalysts or carried out at rigid conditions. ,,, Our newly synthesized catalysts display good performance under much milder conditions than those of reported Co-based catalytic systems. Also, the catalytic activity is even comparable to some most efficient ionic polymer catalysts. , …”

Section: Resultsmentioning

confidence: 91%

“…Previously, the results relative to the Co-based catalysts for the CO 2 cycloaddition of epoxide still relied on adding co-catalysts or carried out at rigid conditions. 19,43,47,48 Our newly synthesized catalysts display good performance under much milder conditions than those of reported Co-based catalytic systems. Also, the catalytic activity is even comparable to some most efficient ionic polymer catalysts.…”

Section: Acs Applied Materials and Interfacesmentioning

confidence: 84%

Cobalt–Salen-Based Porous Ionic Polymer: The Role of Valence on Cooperative Conversion of CO₂ to Cyclic Carbonate

Han

Lin

et al. 2019

ACS Appl. Mater. Interfaces

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Cobalt−salen-based porous ionic polymers, which are composed of cobalt and halogen anions decorated on the framework, effectively catalyze the CO 2 cycloaddition reaction of epoxides to cyclic carbonates under ambient conditions. The cooperative effect of bifunctional active sites of cobalt as the Lewis acidic site and the halogen anion as the nucleophile responds to the high catalytic performance. Moreover, density functional theory results indicate that the cobalt valence state and the corresponding coordination group influence the rate-determining step of the CO 2 cycloaddition reaction and the nucleophilicity of halogen anions.

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Highly active dinuclear cobalt complexes for solvent-free cycloaddition of CO₂ to epoxides at ambient pressure

Abstract: Dinuclear Co-based catalysts are used for the coupling reaction of epoxides and CO2 in the presence of a cocatalyst.

Cited by 43 publications

References 46 publications

Synthesis, Characterization, and Catalytic Study of Amine-Bridged Bis(phenolato) Co(II) and Co(II/III)-M(I) Complexes (M = K or Na)

Synthesis, Characterization, and Catalytic Study of Amine-Bridged Bis(phenolato) Co(II) and Co(II/III)-M(I) Complexes (M = K or Na)

Porous Metallosalen Hypercrosslinked Ionic Polymers for Cooperative CO₂ Cycloaddition Conversion

Cobalt–Salen-Based Porous Ionic Polymer: The Role of Valence on Cooperative Conversion of CO₂ to Cyclic Carbonate

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Highly active dinuclear cobalt complexes for solvent-free cycloaddition of CO2 to epoxides at ambient pressure

Abstract: Dinuclear Co-based catalysts are used for the coupling reaction of epoxides and CO2 in the presence of a cocatalyst.

Cited by 43 publications

References 46 publications

Synthesis, Characterization, and Catalytic Study of Amine-Bridged Bis(phenolato) Co(II) and Co(II/III)-M(I) Complexes (M = K or Na)

Synthesis, Characterization, and Catalytic Study of Amine-Bridged Bis(phenolato) Co(II) and Co(II/III)-M(I) Complexes (M = K or Na)

Porous Metallosalen Hypercrosslinked Ionic Polymers for Cooperative CO2 Cycloaddition Conversion

Cobalt–Salen-Based Porous Ionic Polymer: The Role of Valence on Cooperative Conversion of CO2 to Cyclic Carbonate

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Product

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Highly active dinuclear cobalt complexes for solvent-free cycloaddition of CO₂ to epoxides at ambient pressure

Porous Metallosalen Hypercrosslinked Ionic Polymers for Cooperative CO₂ Cycloaddition Conversion

Cobalt–Salen-Based Porous Ionic Polymer: The Role of Valence on Cooperative Conversion of CO₂ to Cyclic Carbonate