Insight into the Varying Reactivity of Different Catalysts for CO₂ Cycloaddition into Styrene Oxide: An Experimental and DFT Study

The cycloaddition of CO₂ into epoxides to form cyclic carbonates is a highly sought-after reaction for its potential to both reduce and use CO₂, which is a greenhouse gas. In this paper, we present experimental and theoretical studies and a mechanistic approach for three catalytic systems. First, as Lewis base catalysts, imidazole and its derivatives, then as a Lewis acid catalyst, ZnI₂ alone, and after that, the combined system of ZnI₂ and imidazole. In the former, we aimed to discover the reasons for the varied reactivities of five Lewis base catalysts. Furthermore, we succeeded in reproducing the experimental results and trends using DFT. To add, we emphasized the importance of non-covalent interactions and their role in reactivity. In our case, the presence of a hydrogen bond was a key factor in decreasing the reactivity of some catalysts, thus leading to lower conversion rates. Finally, mechanistically understanding this 100% atom economy reaction can aid experimental chemists in designing better and more efficient catalytic systems.