Herein we present a series of new alpha-iminopyridine-based iron-PNN pincer complexes [FeBr2LPNN] (1), [Fe(CO)(2)L-PNN] (2), [Fe(CO)(2)L-PNN](BF4) (3), [Fe(F)-(CO)(2)L-PNN](BF4) (4), and [Fe(H)(CO)(2)L-PNN](BF4) (5) with formal oxidation states ranging from Fe(0) to Fe(II) (L-PNN = 2-[(di-tert-butylphosphino)methyl]-6-[1-(2,4,6-mesitylimino)ethyl]pyridine). The complexes were characterized by a variety of methods including H-1, C-13, N-15, and P-31 NMR, IR, Mossbauer, and X-ray photoelectron spectroscopy (XPS) as well as electron paramagnetic resonance (EPR) and magnetic circular dichroism (MCD) spectroscopy, SQUID magnetometry, and X-ray crystallography, focusing on the assignment of the metal oxidation states. Ligand structural features suggest that the alpha-iminopyridine ligand behaves as a redox non-innocent ligand in some of these complexes, particularly in [Fe(CO)(2)L-PNN] (2), in which it appears to adopt the monoanionic form. In addition, the NMR spectroscopic features (C-13, N-15) indicate the accumulation of charge density on parts of the ligand for 2. However, a combination of spectroscopic measurements that more directly probe the iron oxidation state (e.g., XPS), density functional theory (DFT) calculations, and electronic absorption studies combined with time-dependent DFT calculations support the description of the metal atom in 2 as Fe(0). We conclude from our studies that ligand structural features, while useful in many assignments of ligand redox non-innocence, may not always accurately reflect the ligand charge state and, hence, the metal oxidation state. For complex 2, the ligand structural changes are interpreted in terms of strong back-donation from the metal center to the ligand as opposed to electron transfer.