CO2 to Cyclic Carbonate: A Mechanistic Insight of a Benign Route Using Zinc(II) Salophen Complexes

Abstract Zinc(II) Schiff base complexes with different substituents at 5, 5’ positions have been synthesized to study the effect of the electronic environment of the metal towards the cycloaddition reaction between CO 2 and epoxide. The complexes have been characterized by FT‐IR, XPS, NMR, electronic spectroscopy, LC–MS, and TGA. We have used density functional theory to study the electronic structure of the Zn(II) complexes and modelled the electronic spectra and the mechanism of catalysis. Results obtained from DFT and LC–MS indicate the dimeric structures for all the complexes except ZnL4. The monomeric ZnL4 has the strongest electron withdrawing group, i. e., −NO 2 at 5, 5’ positions along with two labile water molecules attached to the Zn center. The dimeric complexes exhibit good to moderate yield for cycloaddition reaction to styrene carbonate under solvent‐free conditions and a relatively low reaction temperature of 80 °C, with CO 2 pressure of ~1 atm. The best yield has been achieved by ZnL4. Different rate‐determining steps are captured by the DFT studies for dimeric and monomeric complexes. Without taking any preventing measure of dimerization by attaching the bulky t Bu groups, relatively lesser catalytic amounts of all the complexes have shown yields of cyclic carbonate between 53–74 %, depending on the nature of the substituent present.