Incorporation of the triad of redox activity, hemilability, and proton responsivity into a single ligand scaffold is reported. Due to this triad, the complexes Fe((PDI)-P-PYrr)(CO)(2) (3) and Fe((PDI)-P-Mor)(CO)(2) (4) display 40-fold enhancements in the initial rate of NO2- reduction, with respect to Fe((PDI)-P-MeO)(CO)(2) (7). Utilizing the proper sterics and pK(a) of the pendant base(s) to introduce hemilability into our ligand scaffolds, we report unusual {FeNO}(x) mononitrosyl iron complexes (MNICs) as intermediates in the NO2- reduction reaction. The {FeNO}(x) species behave spectroscopically and computationally similar to {FeNO}(7), an unusual intermediate-spin Fe(III) coupled to triplet NO- and a singly reduced PDI ligand. These {FeNO}(x) MNICs facilitate enhancements in the initial rate.