Several new diphenylamino- and diphenylphosphanyldialkylalanes are reported, which were characterized in solution and in the solid state, assisted by in-depth bonding analysis within the DFT framework. In the case of bulky alkyl substituents on the aluminum atom, the species are stable in their monomeric form and were structurally characterized by single crystal X-ray diffraction, expanding the relatively small field of monomeric pnictogenylalanes. In the case of oligomeric diphenylpnictogenyldimethylalanes, their reactivity toward different σ-donor ligands was studied, and several examples of monomeric adducts could be structurally characterized, including the first cyclic(alkyl)(amino)carbene complexes. The reactivity of these CAAC complexes, their oligomeric precursors, and an unstabilized monomeric aminoalane toward CO2 was probed, leading to different insertion products that could be characterized. Additionally, the mechanism was elucidated by DFT calculations.