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Metal complexes composed of redox-active pyridinediimine (PDI) ligands are capable of forming ligand-centered radicals. In this Forum article, we demonstrate that integration of these types of redox-active sites with bioinspired secondary coordination sphere motifs produce direduced complexes, where the reduction potential of the ligand-based redox sites is uncoupled from the secondary coordination sphere. The utility of such ligand design was explored by encapsulating redox-inactive Lewis acidic cations via installation of a pendant benzo-15-crown-5 in the secondary coordination sphere of a series of Fe(PDI) complexes. Fe( 15bz5 PDI)(CO) 2 was shown to encapsulate the redox-inactive alkali ion, Na + , causing only modest (31 mV) anodic shifts in the ligand-based redox-active sites. By uncoupling the Lewis acidic sites from the ligand-based redox sites, the pendant redox-inactive ion, Na + , can entice the corresponding counterion, NO 2  - , for reduction to NO. The subsequent initial rate analysis reveals an acceleration in anion reduction, confirming this hypothesis.

Uncoupled Redox-Inactive Lewis Acids in the Secondary Coordination Sphere Entice Ligand-Based Nitrite Reduction