A DFT-design of single component bifunctional organocatalysts for the carbon dioxide/propylene oxide coupling reaction.

The aim of this work is to develop single-component bifunctional organic catalysts capable of effective coupling reactions between CO2 and propylene epoxide (PO) under mild conditions using density functional theory (DFT) calculations. The dual functionalities of the target catalysts come from their inclusion of a hydroxyl-containing electrophile and the nucleophilicity of iodide ion. In this respect, a series of hydroxyl-functionalized quaternary onium-based ionic liquids were studied using M062X-D3/def2-TZVP//M062X-D3/def2-SVPP model chemistry. The design of catalysts was based on tailoring two structural factors; the first one is the onium center of pnictogens (N, P, As, Sb and Bi), and the second one is the number of hydrogen bond donor groups ( = 1-3). The proposed catalysts were examined by investigation of their catalytic mechanisms to afford the cyclic carbonate. Additionally, the highest active transition state, along with the potential energy difference, was examined using non-covalent interaction (NCI) analysis. Also, the activation strain model (ASM) was used to explain the kinetic behavior of PO activation. The findings showed that the ring-opening step of PO is always the critical step of the reaction. Among the suggested catalysts, the results indicated that the dihydroxyl ammonium-based catalyst (2OH-NI) is a good choice for this catalysis under mild and solvent-free conditions.