Reactions of the "digallene" Ar'GaGaAr'(1) (Ar' = C6H3-2,6-(C6H3-2,6-Pr-2(i))(2)), which dissociates to green : GaAr' monomers in solution, with unsaturated N-N-bonded molecules are described. Treatment of solutions of : GaAr' with the bulky azide N3Ar# (Ar-# = C6H3-2,6-(C6H2-2,6-Me-2-4-Bu-t)(2)), afforded the red imide Ar' GaNAr# (2). Addition of the azobenzenes, ArylNNAryl (Aryl = C6H4-4-Me (p-tolyl), mesityl, and C6H3-2,6-Et-2) yielded the 1,2-Ga2N2 ring compound Ar'GaN(p-tolyl)N(p-tolyl)GaAr' (3) or the products MesN= NC6H2-2,4-Me-2-6-Ga(Me)Ar' (4) and 2,6-Et2C6H3NdNC6H3-2-Et-6-Ga(Et) Ar' (5). Reaction of GaAr' with N2CPh2 yielded the 1,3-Ga2N2 ring compound Ar'Ga(mu:eta(1)-N2CPh2)(2)GaAr' (6), which is quasi-isomeric to 3. Calculations on simple model isomers showed that the Ga(I) amide GaNR2 (R = Me) is much more stable than the isomeric Ga(III) imide RGaNR. This led to the synthesis of the first stable monomeric Ga(I) amide, GaN(SiMe3)Ar" (8) (Ar" = C6H3-2,6-(C6H2-2,4,6-Me-3)(2) from the reaction of LiN(SiMe3)Ar" (7) and "GaI". Compound 8 is also the first one-coordinate gallium species to be characterized in the solid state. The reaction of 8 with N3Ar" afforded the amido-imide derivative Ar"NGaN(SiMe3)Ar" (9), a gallium nitrogen analogue of an allyl anion. All compounds were spectroscopically and structurally characterized. In addition, DFT calculations were performed on model compounds of the amide, imide, and cyclic 1,2- and 1,3-species to better understand their bonding. The pairs of compounds 2 and 8 as well as 3 and 6 are rare examples of quasi-isomeric heavier main group element compounds.