Tolman has shown the influences of nearby cations on O-H bond dissociation energies. In more recent work, Tomson observed shifts in redox potentials that were attributed to stabilization of a dz 2 orbital, and supported this idea with DFT calculations. Redox potentials were primarily used to probe cation effects in these examples, but incorporation of iron in our complexes enabled us to use Mössbauer spectra that can be directly related to the electronic structure of iron. Through the combination of spectroscopy and DFT, we identified cation-dependent changes in orbital energetics. While the overall spin state is conserved throughout, a b electron shifts to a cationstabilized dz 2 orbital, manifested in Mössbauer spectra by low δ and |ΔEQ|. In the future, this effect may be utilized to control reactivity that depends on the ordering of orbital energies.