Unravelling the Mechanism of CO2 Activation: Insights Into Metal-Metal Cooperativity and Spin-Orbit Coupling with {3d-4f} Catalysts.

Converting CO2 into useful chemicals using metal catalysts is a significant challenge in chemistry. Among the various catalysts reported, transition metal lanthanide hybrid {3d-4f} complexes stand out for their superior efficiency and site selectivity. However, unlike transition metal catalysts, understanding the origin of this efficiency in lanthanides poses a challenge due to their orbital degeneracy, rendering the application of DFT methods ineffective. In this study, we employed a combination of density functional theory (DFT) and ab initio CASSCF/RASSI-SO calculations to explore the mechanism of CO2 conversion to cyclic carbonate using a 3d-4f heterometallic catalyst for the first time. This work unveils the importance of 3d and 4f metal cooperativity and the role of individual spin-orbit states in dictating the overall efficiency of the catalyst.