The novel compounds (MeAlNC(6)F(5))4 1, MeS(2)AlNHC(6)F(5) 2, Mes(2)GaNHC(6)F(5) 3, and NHC6F5Ga(MesGa)(3)(mu(3)-NC6F5)(4) 4 of group 13 have been prepared in high yields by the reaction of Me(3)Al; Mes(3)Al, and Mes(3)Ga with pentafluoroaniline, respectively. 1-4 have been fully characterized by elemental analysis, IR, NMR, and mass spectrometry. The crystal structures of 1 and 4 have been determined. 1.0.5hexane crystallizes in the space group P (1) over bar, a = 1594.1(5) pm, b = 1643.0(5) pm, c = 1777.0(6)pm a = 66.81(1)degrees, beta = 63.77(1)degrees, gamma = 64.16-(1)degrees, V = 3.639(2)nm(3-), Z = 4, and R = 0.0507 (wR2 = 0.1294); 4 crystallizes in the space group C2/c, a = 4532.4(1) pm, b = 1207.7(4) pm, c = 2246.2(5) pm, a gamma = 90 degrees, beta = 91.92(3), V = 12.288(6) nm(3), Z = 8, and R = 0.0576 (wR2 = 0.1172). The structure of 1 displays an almost perfect cube with alternating aluminum and nitrogen atoms. In contrast 4 consists of a distorted cube. 4 is the first example of an amino-substituted iminogallane containing a heterocubane structure. According to a modified Schomaker-Stevenson equation a bond order of 1 can be attributed to the exocyclic Ga(2)-N(5) bond length, whereas the Ga-N distances within the core have bond orders of 2/3.