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

IIQ

Helena Corona, Marina Perez-Jimenez, Felipe de la Cruz- Martínez, Israel Fernández, y Jesus Campos. Angew. Chem. Int. Ed. 2022, Vol. 0, e202207581

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)₂Fe] (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(PMe₂Ar)]+ irreversibly dissociates CO₂, Zn(C₆F₅)₂ and B(C₆F₅)₃ yield different CO₂ adducts stabilized by push-pull interactions, while Al(C₆F₅)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.

https://doi.org/10.1002/anie.202207581