Spin, oxidation, and ligand states of p-nitrothiophenolatoiron(III) complex of protoporphyrin-IX-dimethylester in the presence of 1-MeIm: magnetic circular dichroism and 1H nuclear magnetic resonance spectroscopic studies.
Complex formation of 5-coordinated iron(III) heme containing thiolate anion (p-nitrothiophenol) with imidazole (1-methylimidazole) showed very interesting features depending on the nature of the solvent and the ratio of the ligand to heme. The complexes formed under different conditions were not only low spin iron(III) complexes with a thiolate anion and an imidazole or with two imidazoles, but also reduced (iron(II] complexes with a thiolate and an imidazole or with two imidazoles. Absorption, magnetic circular dichroism, and 1H NMR spectroscopies could identify the complex formed when they were used concurrently. The dependence of polarity of the solvents used on the resultant chemical species was ascribed to the stability of Fe(III) or Fe(II) complex in the different solvents. The iron(III) complex with a thiolate anion and an imidazole was found to be reduced automatically to the iron(II) complex with a thiolate and an imidazole which exchanged ligand to the iron(II) bisimidazoles in the presence of excess imidazole. This study showed that the ligands of heme are easily exchanged and that the heme iron(III) is automatically reduced in several conditions. Possible significance with respect to biological systems containing a sulfur ligand is discussed.
D002942:Circular Dichroism; D003580:Cytochromes / Q000378:metabolism; D007093:Imidazoles; D009682:Magnetic Resonance Spectroscopy / Q000379:methods; D008280:Magnetics; D008665:Metalloporphyrins; D008954:Models, Biological; D009211:Myoglobin / Q000378:metabolism; D011166:Porphyrins; D011524:Protoporphyrins
D003580:Cytochromes; D007093:Imidazoles; D008665:Metalloporphyrins; D009211:Myoglobin; D011166:Porphyrins; D011524:Protoporphyrins; C052158:(4-nitrothiophenolato)iron(III)-protoporphyrin IX dimethyl ester complex; C018100:1-methylimidazole; C041104:dimethyl protoporphyrin IX