A series of Group 13 halide complexes of Sb n Bu3, [GaX3(Sb n Bu3)] and [InX3(Sb n Bu3)] (X = Cl, Br , I) have been prepared by reaction of the appropriate trihalide with Sb n Bu3 in n-hexane or CH2Cl2 solution, and characterised by microanalysis, IR, 1 H, 13 C{ 1 H} and 71 Ga NMR spectroscopy. X-Ray crystal structures are reported for [InX3(Sb n Bu3)] (X = Cl, Br) and [GaX3(Sb n Bu3)]. Similar pseudotetrahedral complexes of AsEt3, [GaCl3(AsEt3)], [InCl3(AsEt3)] and the five-coordinate [InCl3(AsEt3)2] were also obtained and their structures determined. Attempts to use [InCl3(SbR3)] and [GaCl3(SbR3)] (R = n Bu, Et) as single source precursors for low pressure CVD growth of InSb or GaSb films were unsuccesful, instead producing elemental antimony, while [GaCl3(AsEt3)] and [InCl3(AsEt3)] failed to produce any deposition under similar conditions.