Nucleophilic ring-opening of iron(iii)-hydroxy-isoporphyrin

Abstract

The reactions of iron(III) hydroxyisoporphyrin, chloro[5-(hydroxy)-5,10,15,20-tetrakis(4-methyl)-5,21H-porphinato]iron(III) [Fe(4-Me-HTPI)(Cl)]⁻, 1 and chloro[5-(hydroxy)-5,10,15,20-tetrakis(4-methoxy-5,21H-porphinato]iron(III) [Fe(4-OMe-HTPI)(Cl)]⁻, 2 with different O⁻, N⁻ and S⁻ nucleophiles have been performed to understand the reactivity of iron isoporphyrins with nucleophiles. The treatment of iron(III) hydroxy isoporphyrin with alcohols is found to form ring opened 19-benzoyl-1-alkoxy-bilin iron complexes. When alkyl amines were used the formation of ring opened 19-benzoyl-1-alkylamine-bilin iron complexes was observed, but heterocyclic N-nucleophiles such as pyridine and imidazole form benzoyl bilinone iron complexes. No role of oxygen was found in these nucleophilic ring opening reactions. The treatment of a S-nucleophile such as PhSH is found to reduce iron(III)-hydroxyisoporphyrin in the parent iron(III) porphyrin compound. The ring opening products were characterized using electronic and ESI-mass spectroscopy. The mechanism for the formation of ring opening products is based on the formation of a tetrahedral intermediate at the carbon atom near the saturated meso carbon atom similar to the hydrolytic pathway of verdoheme conversion to biliverdin.