Metal-ligand cooperation is an important aspect in earth-abundant metal catalysis. Utilizing ligands as electron reservoirs to supplement the redox chemistry of the metal has resulted in many new exciting discoveries. Here, we demonstrate that iron bipyridine-diimine (BDI) complexes exhibit an extensive electron-transfer series that spans a total of five oxidation states, ranging from the trication [Fe(BDI)]³⁺ to the monoanion [Fe(BDI]^-1. Structural characterization by X-ray crystallography revealed the multifaceted redox noninnocence of the BDI ligand, while spectroscopic (e.g., ⁵⁷Fe Mössbauer and EPR spectroscopy) and computational studies were employed to elucidate the electronic structure of the isolated complexes, which are further discussed in this report.

We report the synthesis, characterization, and reactivity of [LFe₃ (PhPz)₃ OMn(^s PhIO)][OTf]_x (3: x=2; 4: x=3), where 4 is one of very few examples of iodosobenzene-metal adducts characterized by X-ray crystallography. Access to these rare heterometallic clusters enabled differentiation of the metal centers involved in oxygen atom transfer (Mn) or redox modulation (Fe). Specifically, ⁵⁷ Fe Mössbauer and X-ray absorption spectroscopy provided unique insights into how changes in oxidation state (Fe^III₂ Fe^II Mn^II vs. Fe^III₃ Mn^II ) influence oxygen atom transfer in tetranuclear Fe₃ Mn clusters. In particular, a one-electron redox change at a distal metal site leads to a change in oxygen atom transfer reactivity by ca. two orders of magnitude.