Dissociation role on the catalytic activity of organic halides in CO2 conversion to cyclic carbonates: Experimental and computational study

There is a limited number of systematic CO 2 conversion studies that provide a clear understanding of the effect of the active sites of catalysts. Hence, this work examines the catalytic activity of 24 organic salts consisting of chloride, bromide or iodide anions and imidazolium, ammonium, or phosphonium-based cations, in the synthesis of hexylene and styrene carbonates from CO 2 , resulting in a diverse range of yields. The findings revealed that high yields depend heavily on catalyst solubility in the reaction medium, but solubility alone does not guarantee reaction success. This finding supports the new hypothesis that catalyst dissociation, reliant on solubility, is a critical factor in defining the catalytic activity. A strong correlation was observed between carbonate yields and the dissociation constants of catalysts, calculated using the COSMO-RS method. This suggests that greater dissociation, reflecting weaker cation-anion interactions, facilitates the anion nucleophilic attack on the epoxide. Also, the relationship between calculated dissociation constant and experimental ionic conductivity was successfully validated. This highlights the significance of organic salt dissociation on catalytic performance and validates the use of computational tools to predict key operational parameters, enhancing the understanding and optimization of CO 2 conversion into cyclic carbonates. • Systematic study of 24 organic salts to synthesize hexylene and styrene carbonates from CO 2. • Demonstration of the importance of catalyst solubility and dissociation in the epoxide. • Strong correlation between experimental yields and computationally calculated dissociation constants of catalysts. • Consistency between calculated dissociation constants and experimental ionic conductivity.