Redox noninnocent ligands are known to be involved in altering the overall electronic nature of organometallic complexes by serving as an electron reservoir. Pyrazine(diimine) backbones in these complexes introduce enhanced π acidity over their more well-studied pyridine(diimine) analogues and open up the opportunity for functionalization of the nitrogen at the 4-position of the ring. Herein we report the characterization of bis-chelated pyrazine(diimine) [(PzDI)2Fe]n+ (n = 0, 1, and 2) complexes for electronic and structural comparison to pyridine(diimine) complexes (PDI) with similar architectures. Cyclic voltammetry studies show three reductions, two of which are ligand-based and reversible. Reduction of [(PzDI)2Fe]2+ (1) to [(PzDI)2Fe]+ (2) and (PzDI)2Fe (3) gives rise to characteristic structural changes, such as imine C═N bond lengthening, indicating the formation of a ligand radical, a conclusion which is further supported by electron paramagnetic resonance (EPR) and electronic structure calculations. Comparisons between the PzDI and PDI systems are highlighted. Complex 1 can be protonated at the uncoordinated pyrazine nitrogen, resulting in changes to its spectroscopic and redox properties; efforts to further functionalize the ligand are discussed.