Demetalation of (5,10,15,20-Tetraphenylporphyrinato)iron Complexes: Effect of Substituents at the o-Positions of Phenyl Groups

Article abstract of DOI:10.1246/bcsj.64.2289

The demetalation of a series of (5,10,15,20-tetraphenylporphyrinato)iron(III) complexes having bulky substituents at the o-positions of phenyl rings was studied in acetic acid in the presence of iron(II) chloride and HCl.The reaction occurred simultaneously with the reduction of Fe(III) porphyrin to Fe(II) porphyrin, since no demetalation was observed without iron(II) chloride.The pseudo-first-order rate constants, which were determined spectrophotometrically, decreased with an increase in the bulkiness of the o-substituents on the phenyl rings.The atropisomeric structures of the products were determined by high-resolution NMR measurements.