FIG. 27.

ALMO-EDA(solv) results for the additional binding of CO₂ when two positively charged substituents (tetramethylammonium, TMA, and an imidazolium-carrying group denoted as “imid”) are introduced at the ortho position of the meso-phenyl group in FeTPP, a promising molecular catalyst for CO₂ reduction. Compared to unsubstituted FeTPP, the o-TMA groups stabilize CO₂ mainly by alleviating the Pauli repulsion between CO₂ and the FeTPP core, while the o-imid groups stabilize CO₂ primarily through attractive Coulomb interactions. The solvent is acetonitrile (modeled using C-PCM with ɛ = 35.88), and the calculations were performed at the ωB97X-V/def2-TZVPP level of theory.⁶³⁶