Four compounds containing metal−metal quadruple bonds, the [M2(CH3)8]n- ions (M = Cr, Mo, W, Re and n = 4, 4, 4, 2, respectively), have been studied theoretically using multiconfigurational quantum-chemical methods. The molecular structure of the ground state of these compounds has been determined and the energy of the δ → δ* transition has been calculated and compared with previous experimental measurements. The high negative charges on the Cr, Mo, and W complexes lead to difficulties in the successful modeling of the ground-state structures, a problem that has been addressed by the explicit inclusion of four Li+ ions in these calculations. The ground-state geometries of the complexes and the δ → δ* transition have been modeled with either excellent agreement with experiment (Re) or satisfactory agreement (Cr, Mo, and W).