Within the orbital overlap model, a phase rotation of one δ g,u orbital during the dihedral scan is responsible for these sharp differences. The behavior of the corresponding δ g,u orbital pair differs significantly from that of the σ g,u orbitals, which only undergo slight changes in their overlap due to minor structural perturbations in the bent M -O -M bridges or the rotation of the ligand field at one metal center. Changing the M -O -M angle within the restricted range used here does not result in such a severe phase change in the δ g,u orbitals. Despite its smaller overlap by three orders of magnitude, rotating the ligand field at one center over a 60 • range during the dihedral scan induces a complete character inversion in the δ g,u orbitals, thus shifting the character of the δ g orbital from bonding to antibonding character and vice versa. Such a drastic phase change is not induced in these orbitals when the M -O -M angle is varied. A similar trend to the δ g,u orbital pairs is observed for the iron complex in the two π g,u orbital pairs, which remain largely unaffected by the choice of scanning approach. A more detailed analysis of the variations observed across all three coupling paths in the iron complex is shown in the SI.