Mono(Lewis Base)‐Stabilized Gallium Iodide: An Unexplored Class of Promising Ligands

Quantum‐chemical (DFT) calculations on hitherto unknown base(carbene)‐stabilized gallium monoiodides (LB→GaI) suggest that these systems feature one lone pair of electrons and a formally vacant p‐orbital – both centered at the central gallium atom – and exhibit metallomimetic behavior. The calculated reaction free energies as well as bond dissociation energies suggest that these LB→GaI systems are capable of forming stable donor‐acceptor complexes with group 13 trichlorides. Examination of the ligand exchange reactions with iron and nickel complexes indicates their potential use as ligands in transition metal chemistry. In addition, it is found that the title compounds are also able to activate various enthalpically robust bonds. Further, a detailed mechanistic investigation of these small molecule activation processes reveals the non‐innocent behavior of the carbene (base) moiety attached to the GaI fragment, thereby indicating the cooperative nature of these bond activation processes. The energy decomposition analysis (EDA) and activation strain model (ASM) of reactivity were also employed to quantitatively understand and rationalize the different activation processes. Quantum chemical calculations suggest that Lewis base stabilized GaI (LB→GaI) complexes exhibit promising ligand properties and are capable of displaying metallomimetic behavior.