A series of primary amido gallium alkyl complexes that includes a base free dimer, [ t Bu 2 Ga(μ- N( H) t Bu)] 2 ( 1), Lewis base stabilized monomeric complexes, nBu 2Ga(N(H) tBu)(THF) ( 2) and nBu 2Ga[NH(2,6-Me 2C 6H 3)]py ( 3) and an anionic complex, nBu 2Ga[NH(2,6-Me 2C 6H 3)] 2[Li(Et 2O)] ( 4) is reported. Complex 1 crystallizes in the triclinic space group P-1 (a = 10.265(5) A ̊ , b = 15.752(6) A ̊ , c = 8.932(4) A ̊ , α = 90.32(3)°, β = 105.61(3)°, γ = 88.24(4)°) with two molecules, each residing on an inversion center, in the asymmetric unit. Structural analysis revealed a planar Ga 2N 2 core with both the bridging N and the Ga centers in distorted tetrahedral environments (GaC distances 2.052(3)-2.065(3) Å and GaN distances 2.060(3)-2.069(3) Å). The use of excess amido ligand allowed the isolation and crystallization of 4. Complex 4 crystallized in the monoclinic space group P21/n (a = 8.666(2) A ̊ , b = 22.305(3) A ̊ , c = 15.570(3) A ̊ , β = 103.47(2)) with Z = 4. The pseudotetrahedral gallium center has a coordination sphere composed of two amido ligands (GaN1 = 2.011(8) Å, GaN2 = 2.006(7) Å), and two nBu ligands (GaC17 = 2.002(9) Å GaC21 = 1.985(12) Å). A bridging interaction of the lithium cation with the lone pair of electrons on each of amido nitrogen atoms generates a molecular core which is made up of a planar GaN1LiN2 distorted square (N1GalN2 94.4°, GalN2Lil 86.2°, N1Li1N2 92.2°, GalN1Li1 87.1°).