Divergent CO₂ Activation by Tuning the Lewis Acid in Iron-Based Bimetallic Systems

Bimetallic motifs mediate the selective activation and functionalization of CO₂ in metalloenzymes and some recent synthetic systems. In this work, we build on the nascent concept of bimetallic frustrated Lewis pairs (FLPs) to investigate the activation and reduction of CO₂ . Using the Fe⁰ fragment [(depe)₂ Fe] (depe=1,2-bis(diethylphosphino)ethane) as base, we modify the nature of the partner Lewis acid to accomplish a divergent and highly chemoselective reactivity towards CO₂ . [Au(PMe₂ Ar)]⁺ irreversibly dissociates CO₂ , Zn(C₆ F₅ )₂ and B(C₆ F₅ )₃ yield different CO₂ adducts stabilized by push-pull interactions, while Al(C₆ F₅ )₃ leads to a rare heterobimetallic C-O bond cleavage, and thus to contrasting reduced products after exposure to dihydrogen. Computational investigations provide a rationale for the divergent reactivity, while Energy Decomposition Analysis-Natural Orbital for Chemical Valence (EDA-NOCV) method substantiates the heterobimetallic bonding situation.