Iron(III) Complexes with Pyridine Group Coordination and Dissociation Reversible Equilibrium: Cooperative Activation of CO2 and Epoxides into Cyclic Carbonates.

Herein, a series of [ONSN]-type iron(III) complexes were synthesized. A binary catalytic system in combination with iron complexes and tetrabutylammonium bromide (TBAB) exhibited high activity for the synthesis of cyclic carbonates from CO2 (1 atm) and terminal epoxides at room temperature. Additionally, single-component iron complexes without using additional TBAB as nucleophiles also showed high activity for the cycloaddition of CO2 and terminal epoxides under 80 °C and 0.5 MPa of CO2. This study demonstrates that single-component iron catalysts provide a competitive alternative to binary catalytic systems for the synthesis of cyclic carbonates from CO2 and epoxides. Mechanistic studies on a single-component iron catalytic system suggest that the temperature serves as a role of responsive switch for controlling the coordination and dissociation of pyridine bearing iron catalysts detected using in situ infrared spectroscopy, and uncoordinated pyridine activates CO2 to form carbamate. Studies of electrospray ionization high-resolution mass spectrometry reveal that an iron center was used as a Lewis acidic site, free halogen anions from the iron center were used as a nucleophilic site, and coordinated pyridine was released from iron complexes to activate CO2.