Cycloaddition of epoxides and CO₂ catalyzed by bisimidazole-functionalized porphyrin cobalt(iii) complexes

Abstract

Bisimidazole-functionalized cobaltoporphyrin acted as efficient bifunctional catalysts to facilitate the synthesis of cyclic carbonates from epoxides and CO2.

Charged Metalloporphyrin Polymers for Cooperative Synthesis of Cyclic Carbonates from CO2 under Ambient Conditions

“…Herein, based on our previous studies and the rational construction strategy of bifunctional catalysts, aluminum porphyrin‐based ionic porous organic polymers (Al‐iPOPs) were synthesized successfully by a facile one‐pot method. This promising presynthetic technique was based on the typical Yamamoto–Ullmann coupling reaction between 5,10,15,20‐tetrakis(4‐bromophenyl)porphyrin‐aluminum(III) chloride (Al‐TBPP) and brominated ILs, which include 1,3‐bis(4‐bromobenzyl)imidazolium bromide (IL‐1) and 1,3‐bis(4‐bromophenyl)imidazolium bromide (IL‐2; Scheme ).…”

Electronic Tuning of Zinc Porphyrin Catalysts for the Conversion of Epoxides and Carbon Dioxide into Cyclic Carbonates

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Bifunctional Zn II porphyrinc atalysts bearing tributylammonium bromide groups at the meta positions of the meso-phenyl groups showedh igh catalytic activityf or the synthesis of cyclic carbonates from epoxidesand CO 2 .Herein, several substituents with different electronic properties were introduced at the para positions. [3][4][5][6][7][8] Cyclic carbonates can be practically used as raw materials for polycarbonates, electrolytes in lithium-ion secondary batteries,a sf uel additives. The bifunctional catalystb earing cyano groups showed the highest catalytic activity with at urnover frequency of up to 42 000 h À1 .

The chemical fixation of carbon dioxide (CO 2 )a saC1 feedstock into useful organic compounds hasb ecome remarkably important in green and sustainable chemistry.

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“…Introduction of electron-donating groups decreasedt he catalytic activity,w hereast he introductiono fe lectron-withdrawing groups increased the activity.T he substituents modulated the Lewis acidity of the zinc center, which was confirmed by binding constant experiments. To date, variousc atalysts including metal complexes [4][5][6] and organocatalysts [7] have been developed to activate the substrates (i.e.,e poxidesa nd/or CO 2 ). [1,2] The synthesis of cyclic carbonates from epoxides and CO 2 is one of the most valuableCO 2 fixation reactions, and it exhibits ahigh atom efficiency (Scheme 1).…”

“…[1,2] The synthesis of cyclic carbonates from epoxides and CO 2 is one of the most valuableCO 2 fixation reactions, and it exhibits ahigh atom efficiency (Scheme 1). To date, variousc atalysts including metal complexes [4][5][6] and organocatalysts [7] have been developed to activate the substrates (i.e.,e poxidesa nd/or CO 2 ). To date, variousc atalysts including metal complexes [4][5][6] and organocatalysts [7] have been developed to activate the substrates (i.e.,e poxidesa nd/or CO 2 ).…”

Sustainable Cyclic Carbonate Production, Utilizing Carbon Dioxide and Azolate Ionic Liquids

“…1,2 Nevertheless, it offers a virtually inexhaustible, inexpensive, non-flammable and readily available C1 feedstock for organochemical processes. [3][4][5][6][7] The direct conversion of CO2 to five-or six-membered cyclic carbonates [8][9][10] is one of the most promising strategies for producing highly desirable solvents for electrolytes in Li-ion rechargeable batteries. 11,12 Cyclic carbonates are also utilised as monomers in polymerisation reactions, 13,14 as intermediates in the synthesis of fine chemicals 7 and as high boiling aprotic polar solvents.…”