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

Easily available and inexpensive Fe carbamates were employed in the solvent-free synthesis of a series of cyclic carbonates from epoxides and CO 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(O CNEt ) and NBu Br 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.