Excess bioavailable nitrogen species are disrupting the natural nitrogen cycle and leading to environmental crises such as hypoxic zones in coastal waters. Nitrate is among one of the primary pollutants causing these issues. In addition, nitrite is also a recalcitrant contaminant in need of attention. Nature employs metalloenzymes such as nitrite and nitrate reductases to convert these contaminants to more innocuous species. In this work, functional bioinspired complexes based on iron, merged with redox-active hemilabile pyridinediimine ligands will be described. These complexes utilize hemilabile proton acceptors in the secondary coordination sphere to facilitate the binding and reduction of nitrite and nitrate to either Mononitrosyl Iron Complexes (MNICs) and/or Dinitrosyl Iron Complexes (DNICs) (based on the metal ligand scaffold employed). These complexes have been structurally characterized and will be described. Computational work was also performed to aid in the understanding the electronics of these unique, interesting complexes.

Reduction of recalcitrant nitrate and nitrite via mononitrosyl and dinitrosyl iron complexes

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