Unraveling Chlorite Oxidation Pathways in Equatorially Heteroatom-Substituted Nonheme Iron Complexes

The first-coordination sphere of catalysts is known to play a crucial role in reaction mechanisms, but details of how equatorial ligands influence the reactivity remain unknown. Heteroatom ligated to the equatorial position of iron centers in nonheme iron metalloenzymes modulates structure and reactivity. To investigate the impact of equatorial heteroatom substitution on chlorite oxidation, we synthesized and characterized three novel mononuclear nonheme iron(II) complexes with a pentadentate bispidine scaffold. These complexes feature systematic substitutions at the equatorial position in the bispidine ligand framework where the pyridine group is replaced with NMe