Quo Vadis CO₂ Activation: Catalytic Reduction of CO₂ to Methanol Using Aluminum and Gallium/Carbon‐based Ambiphiles

<jats:title>Abstract</jats:title><jats:p>We report on so‐called “hidden FLPs” (FLP: frustrated Lewis pair) consisting of a phosphorus ylide featuring a group 13 fragment in the <jats:italic>ortho</jats:italic> position of a phenyl ring scaffold to form five‐membered ring structures. Although the formation of the Lewis acid/base adducts was observed in the solid state, most of the title compounds readily react with carbon dioxide to provide stable insertion products. Strikingly, 0.3–3.0 mol% of the reported aluminum and gallium/carbon‐based ambiphiles catalyze the reduction of CO<jats:sub>2</jats:sub> to methanol with satisfactory high selectivity and yields using pinacol borane as stoichiometric reduction equivalent. Comprehensive computational studies provided valuable mechanistic insights and shed more light on activity differences.</jats:p>