An isolable monomeric alumylene 2 stabilized by two donating ligands (phosphine and NHC) has been synthesized. Experimental and theoretical analysis confirm that the NHC ligand in 2 is labile and reversibly dissociates from the AlI center above -20 degrees C. Of particular interest, despite being thermodynamically stabilized by two donor ligands, alumylene complex 2 exhibits a high reactivity with a considerably higher nucleophilicity compared to the monophosphine-ligated complex 5. It is interesting to note that 2 reacts immediately with N2O at -90 degrees C, allowing the synthesis of bis-ligated aluminum oxide 15, which is stable up to -70 degrees C.