Mo(S₂C₂(CF₃)₂)₃, 1a, has proven a useful p-dopant in organic electronics. To develop more soluble p-dopants, MoS₉²⁻was treated with alkynes CF₃CCCO₂Me and CF₃CCCOCF₃to give the dianions of the corresponding tris(dithiolene) complexes, 1b²⁻and 1c²⁻, respectively, which were then oxidized to neutral molybdenum tris[1-(methoxycarbonyl)-2-(trifluoromethyl)-ethane-1,2-dithiolene], 1b, and molybdenum tris[1-(trifluoroethanoyl)-2-(trifluoromethyl)ethane-1,2-dithiolene], 1c, using NO⁺PF₆⁻. The crystal structures of (NEt₄⁺)₂1b²⁻, (NEt₄⁺)₂1c²⁻, and neutral 1c have been determined. In all three cases, the metal coordination is approximately trigonal prismatic and the major isomer is cis (approximately C_3v). The structure of 1b²⁻is distorted by a twist towards pseudo-octahedral coordination similar to that seen in structures of 1a²⁻and Mo(S₂C₂(CO₂Me)₂)₃²⁻, 1d²⁻, salts, and that of 1c exhibits marked folds between the planes formed by the ligand atoms and those formed by the Mo and coordinated S atoms, similar to those seen in the structure of 1a. On the other hand, the metal dithiolene core of 1c²⁻is essentially undistorted from C_3vsymmetry. The oxidant strength of the neutral molecules increases in the order 1d < 1b < 1a < 1c, with the potentials ranging from −0.02 to +0.39 V versus the ferrocenium/ferrocene couple.