Experimental matrix IR spectra in alliance with extensive quantum chemical calculations provide a framework for the detailed evaluation of the structures and electronic properties of the doublet species Al.NH3, Al(NH3)(2), HAlNH2, HAlNH2.NH3, and Al(NH2)(2). These species were the products of the reaction of Al atoms with NH3 in an Ar matrix. While the two species Al.NH3 and HAlNH2 were already sighted in previous experiments, the results described herein lead to the first identification and characterization of HAlNH2.NH3 and AI(NH2)(2), the products of the reaction of Al atoms with two NH3 molecules. The results allow a detailed reaction scheme leading to all the product species to be established. The unpaired electron in each of the species Al.NH3, AI(NH3)(2), HAlNH2, HAlNH2.NH3, and AI(NH2)(2) is located near the Al atom, but there is a significant degree of delocalization, especially in Al(NH2)(2), due to pi bonding interactions. The consequences for the barrier to pyramidalization at the N-atom are discussed.