How Innocent are Potentially Redox Non-Innocent Ligands? Electronic Structure and Metal Oxidation States in Iron-PNN Complexes as a Representative Case Study

Herein we present a series of new α-iminopyridine-based iron-PNN pincer complexes [FeBr₂L_PNN] (1), [Fe(CO)₂L_PNN] (2), [Fe(CO)₂L_PNN](BF₄) (3), [Fe(F)(CO)₂L_PNN](BF₄) (4), and [Fe(H)(CO)₂L_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 ¹H, ¹³C, ¹⁵N, and ³¹P NMR, IR, Mössbauer, 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 α-iminopyridine ligand behaves as a redox non-innocent ligand in some of these complexes, particularly in [Fe(CO)₂L_PNN] (2), in which it appears to adopt the monoanionic form. In addition, the NMR spectroscopic features (¹³C, ¹⁵N) 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. (Chemical Equation Presented).