Density functional theory (DFT) calculations have been used to investigate the d(3)d(3) bioctahedral complexes, MM'Cl-9(5-), of the vanadium triad. Broken-symmetry calculations upon these species indicate that the V-containing complexes have optimized metal-metal separations of 3.4-3.5 Angstrom, corresponding to essentially localized magnetic electrons. The metal-metal separations in these weakly coupled dimers are elongated as a consequence of Coulombic repulsion, which profoundly influences (and destabilizes) the gas-phase structures for such dimers; nevertheless, the intermetallic interactions in the V-containing dimers involve significantly greater metal-metal bonding character than in the analogous Cr-containing dimers. These observations all show good agreement with existing experimental (solid state) results for the chloride-bridged, face-shared dimers V2Cl95- and V2Cl3(thf)(6)(+). In contrast to the V-containing dimers, complexes featuring only Nb and Ta have much shorter intermetallic distances (similar to2.4 Angstrom) consistent with d-electron delocalization and formal metal-metal triple bond formation; again, good agreement is found with available experimental data. Calculations on the complexes V-2(mu-Cl)(3)(dme)(6)(+), Nb-2(mu-dms)(3)Cl-6(2-), and Ta-2(mu-dms)(3)Cl-6(2-), which are closely related to compounds for which crystallographic structural data exist, have been pursued and provide an insight into the intermetallic interactions in the experimentally characterized complexes. Analysis of the contributions from d-orbital overlap (E-ovlp) stabilization, as well as spin polarization (exchange) stabilization of localized d electrons (E-spe), has also been attempted for the MM'Cl-9(5-) dimers. While E-ovlp clearly dominates over E-spe, as a stabilizing factor in those dimers containing only Nb and Ta metal atoms, detailed assessment of the competition between E-ovlp and E-spe for V-containing dimers is obstructed by the instability of triply bonded V-containing climers against Coulombic explosion. On the basis of the periodic trends in E-ovlp versus E-spe, the V-triad dimers have a greater propensity for metal-metal bonding than do their Cr-triad or Mn-triad counterparts.