Solvent- and Co-Catalyst-Free Cycloaddition of Carbon Dioxide and Epoxides Catalyzed by Recyclable Bifunctional Niobium Complexes.

CO2, as a cheap and abundant renewable C1 resource, can be used to synthesize high value-added chemicals. In this paper, a series of bifunctional metallic niobium complexes were synthesized and their structures were characterized by IR, NMR and elemental analysis. All of these complexes have been proved to be efficient catalysts for the coupling reaction of CO2 and epoxides to obtain cyclic carbonates under solvent- and co-catalyst-free conditions. By using CO2 and propylene oxide as a model reaction, the optimal reaction conditions were systematically screened as: 100 °C, 1 MPa, 2 h, ratio of catalyst to alkylene oxide 1:100. Under the optimal reaction conditions, the bifunctional niobium catalysts can efficiently catalyze the coupling reaction with high yield and excellent selectivity (maximum yield of >99% at high pressure and 96.8% at atmospheric pressure). Moreover, this series of catalysts can also catalyze the coupling reaction at atmospheric pressure and most of them showed high conversion of epoxide. The catalysts have good substrate suitability and are also applicable to a variety of epoxides including diepoxides and good catalytic performances were achieved for producing the corresponding cyclic carbonates in most cases. Furthermore, the catalysts can be easily recovered by simple filtration and reused for at least five times without obvious loss of catalytic activity and selectivity. Kinetic studies were carried out preliminarily for the bifunctional niobium complexes with different halogen ions (3a(Cl-), 3b(Br-), 3c(I-)) and the formation activation energies (Ea) of cyclic carbonates were obtained. The order of apparent activation energy Ea is 3a (96.2 kJ/mol) > 3b (68.2 kJ/mol) > 3c (37.4 kJ/mol). Finally, a possible reaction mechanism is proposed.

Solvent-Free Coupling Reaction of Carbon Dioxide and Epoxides Catalyzed by Quaternary Ammonium Functionalized Schiff Base Metal Complexes under Mild Conditions.

A series of bifunctional Schiff base metal catalysts (Zn-NPClR, Zn-NPXH, and M-NPClH) with two quaternary ammonium groups were prepared for carbon dioxide (CO2) and epoxide coupling reactions. The effects of the reaction variables on the catalytic activity were systematically investigated, and the optimal reaction conditions (120 °C, 1 MPa CO2, 3 h) were screened. The performances of different metal-centered catalysts were evaluated, and Co-NPClH showed excellent activity. This kind of bifunctional catalyst has a wide range of substrate applicability, excellent stability, and can be reused for more than five runs. A relatively high TOF could reach up to 1416 h-1 with Zn-NPClH as catalyst by adjusting reaction factors. In addition, the kinetic study of the coupling reaction catalyzed by three catalysts (Zn, Co, and Ni) was carried out to obtain the activation energy (Ea) for the formation of cyclic carbonates. Finally, a possible mechanism for this cyclization reaction was proposed.

Functionalized ß-Cyclodextrins Catalyzed Environment-Friendly Cycloaddition of Carbon Dioxide and Epoxides.

Ammonium, imidazole, or pyridinium functionalized ß-cyclodextrins (ß-CDs) were used as efficient one-component bifunctional catalysts for the coupling reaction of carbon dioxide (CO2) and epoxide without the addition of solvent and metal. The influence of different catalysts and reaction parameters on the catalytic performance were examined in detail. Under optimal conditions, Im-CD1-I catalysts functionalized with imidazole groups were able to convert various epoxides into target products with high selectivity and good conversion rates. The one-component bifunctional catalysts can also be recovered easily by filtration and reused at least for five times with only slight decrease in catalytic performance. Finally, a possible process for hydroxyl group-assisted ring-opening of epoxide and functionalized group- induced activation of CO2 was presented.