869779-57-7Relevant academic research and scientific papers
Direct incorporation of a ferric ion in the porphyrinogen core: Tetrakis(cyclohexyl)iron porphyrinogen anion with different conformers and its reaction with iodine
Bhattacharya, Dibyendu,Dey, Soumen,Maji, Suman,Pal, Kuntal,Sarkar, Sabyasachi
, p. 7699 - 7701 (2005)
Et4N[L″TeIII]·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 (μeff) of 4.3 μB in the solid, which changed to 6.0 μB 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″TeIII]·DCM 0.5Py1.5 (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″γγFeIII][I 3·I2+·I3-] (3) with the introduction of two Cα-Cα bonds with concomitant reduction of Fe(III) to Fe(II). Its μeff (5.4 μB) in the solid changed to 4.8 μB in solution, suggesting a high spin state (S = 2) for Fe(II).
