Iron(III) N,N-Dialkylcarbamate-Catalyzed Formation of Cyclic Carbonates from CO2 and Epoxides under Ambient Conditions by Dynamic CO2 Trapping as Carbamato Ligands

Easily available and inexpensive FeIII carbamates were employed in the solvent‐free synthesis of a series of cyclic carbonates from epoxides and CO2 at room temperature and atmospheric pressure, in the presence of a cocatalyst. Different experimental conditions (type and concentration of catalyst and cocatalyst, as well as reaction time) were investigated: Fe(O2CNEt2)3 and NBu4Br acted as the best catalyst/cocatalyst combination, allowing the formation of propylene carbonate and 1,2‐butylene carbonate with quantitative yield and selectivity in 24 h. According to NMR and DFT studies, the reaction proceeds with the dynamic trapping of carbon dioxide as a carbamato ligand.