The ligand dependence of metal-metal bonding in the d(3)d(3) face-shared M2X9n- (M-III = Cr, Mo, W; M-IV = Mn, Te, Re; X = F, Cl, Br, I) dimers has been investigated using density functional theory. In general, significant differences in metal-metal bonding are observed between the fluoride and chloride complexes involving the same metal ion, whereas less dramatic changes occur between the bromide and iodide complexes and minimal differences between the chloride and bromide complexes. For M = Mo, Tc, and Re, change in the halide from F to I results in weaker metal-metal bonding corresponding to a shift from either the triple metal-metal bonded to single bonded case or from the latter to a nonbonded structure. A fragment analysis performed on M2X93- (M = Mo, W) allowed determination of the metal-metal and metal-bridge contributions to the total bonding energy in the dimer. As the,halide changes from F to I, there is a systematic reduction in the total interaction energy of the fragments which can be traced to a progressive destabilization of the metal-bridge interaction because of weaker M-X-bridge - bonding as fluoride is replaced by its heavier congeners. In contrast, the metal-metal interaction remains essentially constant with change in the halide.