A DFT Study on the Co‐polymerization of CO 2 and Ethylene: Feasibility Analysis for the Direct Synthesis of Polyethylene Esters

The co‐polymerization of CO 2 with the non‐polar monomer ethylene, though highly desirable, still presents a challenge whereas the palladium‐catalyzed CO/C 2 H 4 co‐polymerization is well understood. Building on this analogy, the goal of this study was to elucidate the feasibility of developing suitable catalysts for co‐polymerizing CO 2 with ethylene to polyethylene esters. Computational methods based on density functional theory were hereby employed. In the search for new catalyst lead structures, a closed catalytic cycle was identified for the palladium‐catalyzed CO 2 /C 2 H 4 co‐polymerization reaction. The computational study on palladium complexes with a substituted anionic 2‐[bis(2,4‐dimethoxyphenyl)‐phosphine]‐benzene‐2‐hydroxo ligand revealed key aspects that need to be considered when designing ligand sets for potential catalysts for the non‐alternating co‐polymerization of CO 2 and ethylene.