The removal of an electron from ligand-based orbitals in both [Re2-Model] 0 and [Os2-Model] 0 complexes agreeing with the cyclic voltammetry measured by Ghosh and co-workers. The first oxidation potentials were found to be nearly identical for both metals (0.51 V for Re and 0.55 V for Os) suggesting the removal of the electron occurs the same type of orbital. Furthermore, the computed metal-metal bond distances in both systems are slightly changed upon first oxidation compared to neutral molecules confirming the removal is indeed from the ligand-based orbital. (-0.55 V for Re and -1.31 V for Os). The difference in reduction potentials suggests electron addition into a different type of orbitals; this is consistent with our finds.