Beschreibung:
<jats:title>Abstract</jats:title><jats:p>Bimetallic motifs mediate the selective activation and functionalization of CO<jats:sub>2</jats:sub> 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 CO<jats:sub>2</jats:sub>. Using the Fe<jats:sup>0</jats:sup> fragment [(depe)<jats:sub>2</jats:sub>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 CO<jats:sub>2</jats:sub>. [Au(PMe<jats:sub>2</jats:sub>Ar)]<jats:sup>+</jats:sup> irreversibly dissociates CO<jats:sub>2</jats:sub>, Zn(C<jats:sub>6</jats:sub>F<jats:sub>5</jats:sub>)<jats:sub>2</jats:sub> and B(C<jats:sub>6</jats:sub>F<jats:sub>5</jats:sub>)<jats:sub>3</jats:sub> yield different CO<jats:sub>2</jats:sub> adducts stabilized by push‐pull interactions, while Al(C<jats:sub>6</jats:sub>F<jats:sub>5</jats:sub>)<jats:sub>3</jats:sub> 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.</jats:p>