Carbon Dioxide Cycloaddition to Epoxides Promoted by Nicotinamidium Halide Catalysts: A DFT Investigation

Abstract

AbstractThe utilization of CO2as building block for the production of cyclic carbonate is a promising route to simultaneously mitigate the global warming issue and obtain valuable commercial chemicals. In this work, the activity of nicotinamidium halide catalysts towards the CO2conversion into cyclic carbonate has been explored by means of density functional theory (DFT) calculations. DFT calculations support the ability, suggested experimentally, of the pyridium α‐C−H proton of the catalysts to activate the epoxide ringviaa hydrogen bond. Interestingly, DFT calculations underline the involvement of then‐octyl substituent of the pyridyl ring in the epoxide activation, while the hydrogen atom of the amide group N−H is rather involved in the stabilization of the iodide trough electrostatic interactions. Moreover, the replacement of the pyridium α‐C−H proton with the bulkier methyl group leads to a different reaction mechanism. The calculated energy barriers well reproduce the experimental trends of the studied catalysts, and the computed activation barrier of 29.0 kcal/mol, relative to the ring opening step of the most active catalyst, is in line with the experimental working temperature of 80 °C. Those results shed light on the CO2fixation reaction contributing to the development of more efficient catalytic systems.