Et4N[L"Fe-III](.)3DCM (1) is directly synthesized by adding ferric chloride into a solution of a lithium salt of tetrakis(cyclohexyl)-porphyrinogen (L"). [L"](4-) is a good chelating ligand for both Fe(III) and Fe(II) ions. It is an avid proton scavenger but not a reducing agent. 1 showed a magnetic moment (mu(eff)) of 4.3 mu(B) in the solid, which changed to 6.0 mu(B) in solution. This change in spin state is common for all iron porphrinogens. 1 showed polymorphism, and with pyridine in the lattice, it changed to Et4N-[L" Fe-III](DCM0.5Py1.5)-D-. (2), possessing two different conformers. Calculation of these conformers at the density functional theory level showed the relative energies of all d orbital changes in three conformers, highlighting the influence of the disposition of a peripheral ligand. Iodine oxidation of 1 yielded [L"Fe-Delta Delta(II)][(I3I2+.I3-)-I-.] (3) with the introduction of two C-alpha-C-alpha bonds with concomitant reduction of Fe(III) to Fe(II). Its mu(eff) (5.4 mu(B)) in the solid changed to 4.8 mu(B) in solution, suggesting a high spin state (S = 2) for Fe(II).