Highly oxidized or, "high-valent," first row transition metal complexes are frequently proposed as key species in transformations such as C—H activation/amination and C—C bond formation. In contrast, there exist numerous examples of stable and unreactive species whose metal centers would be considered similarly "high-valent." The factors that dictate the observed reactivity and/or stability of these species remain puzzling, and methods to experimentally analyze electronic structure can yield conflicting results. This thesis combines multi-edge X-ray absorption spectroscopy and computational methods scrutinize oxidation state formalisms and their relationship to reactivity and experimental electronic structure. Advantages and applications of metal K-edge, metal L2,3-edge and ligand K-edge will be presented, and computational methods including density functional theory (DFT), time dependent-DFT, restricted-open-shell configuration interaction (CI) with singles, and spectroscopically oriented CI will be used to guide interpretation of these experimental methods. We will explore the hypothesis that the reactivity profiles of first row transition metal species can be tied inverted ligand fields—where the ligand, not the metal, provides the major source of electrons lost during oxidation. We further expose that redox neutrality is maintained at the metal center, and that the driving force for reactivity can be explained by charge localization, hole character, or radical species on the ligand. Combined this work represents the first efforts to forge connections between ligand field inversion, oxidation state, and observed reactivity. The results contained within will help guide further efforts in catalyst design, materials science, and mechanistic definition of biologically relevant transformations.