Experimental and Computational Studies of Amido Chlorogermylenes as Lewis Acids in CO₂ Insertion

Abstract A novel combination of an amido‐stabilised chlorogermylene (RGeCl) and a cyclic (alkyl)(amino)carbene (cAAC) has been utilized in a frustrated Lewis pair‐type reaction to activate and capture CO 2 . The synthesis, characterization, and reactivity studies accompanied by extensive computational input reveal “push‐pull”‐type interactions in the isolated CO 2 ‐captured compounds. Both the steric and electronic factors as well as the Lewis acidity/basicity are found to play an important role in the reactivity and ability of the FLPs to activate CO 2 . The results indicate that the covalent interaction between the cAAC carbene carbon and electrophilic CO 2 ‐carbon is too strong to facilitate further reduction or reactivity of the bound CO 2 ‐moiety. However, the interaction between the Lewis acidic Ge‐species and the nucleophilic O‐atom of CO 2 shows that germylenes can be utilised as the Lewis acidic partner in FLP‐type chemistry and small molecule activation.