The reaction between GaCl3 and 1 equiv of HN(SiMe2Ph)(2) in CH2Cl2 solution affords colorless crystals of [Cl2Ga{mu -N(H)SiMe2Ph}](2) (1). The related reaction between GaCl3 and 1 equiv of LiN(SiMe2Ph)(2) in hexane solution results in the isolation of colorless crystals of [PhGa{N(SiMe2Ph)(2)}(mu -Cl)](2) (2). In contrast, treatment of GaCl3 with 1 equiv of N(SiMe3)(3) in CH2Cl2 solutions affords colorless crystals of [MeGaCl2](2) (4). Compounds 2 and 4 are the result of monochloride substitution and transfer of a phenyl and methyl ligand, respectively, from the silyl group of the amine to the Ga center. All the complexes have been characterized by X-ray crystallography.