title: Synthesis, characterization, and reactivity of hypochloritoiron(III) porphyrin complexes.
abstract: A hypochloritoiron(III) porphyrin species has been proposed as a key intermediate in an antimicrobial defense system in neutrophils and in heme-catalyzed chlorination reactions. We report herein the preparation, spectroscopic characterization, and reactivity of the bis(hypochlorito)iron(III) porphyrin complex [(TPFP)Fe(III)(OCl)(2)](-) (1) and the imidazole-hypochloritoiron complexes (TPFP)Fe(III)(OCl)(1-R-Im) [R = CH(3) (2), H (3), CH(2)CO(2)H (4)], in which TPFP is 5,10,15,20-tetrakis(pentafluorophenyl)porphyrinate. The structures of 1-4 were confirmed by absorption, (2)H and (19)F NMR, EPR, and resonance Raman spectroscopy and electrospray ionization mass spectrometry at low temperature. The reactions of 1 and 2 with various organic substrates show that 1 and 2 are capable of chlorination, sulfoxidation, and epoxidation reactions and that 1 is much more reactive with these substrates than 2.
authors.affiliation: Institute for Molecular Science and Okazaki Institute for Integrative Bioscience, National Institutes of Natural Sciences, Myodaiji, Okazaki 444-8787, Japan.
authors.forename: Zhiqi
authors.initials: Z
authors.lastname: Cong
authors.forename: Sachiko
authors.initials: S
authors.lastname: Yanagisawa
authors.forename: Takuya
authors.initials: T
authors.lastname: Kurahashi
authors.forename: Takashi
authors.initials: T
authors.lastname: Ogura
authors.forename: Satoru
authors.initials: S
authors.lastname: Nakashima
authors.forename: Hiroshi
authors.initials: H
authors.lastname: Fujii
mesh_terms: D004852:Epoxy Compounds / Q000737:chemistry; D005290:Ferric Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D054879:Halogenation; D006843:Hydrocarbons, Chlorinated / Q000138:chemical synthesis / Q000737:chemistry*; D006997:Hypochlorous Acid / Q000138:chemical synthesis / Q000737:chemistry*; D007093:Imidazoles / Q000138:chemical synthesis / Q000737:chemistry*; D011166:Porphyrins / Q000138:chemical synthesis / Q000737:chemistry*; D013057:Spectrum Analysis; D013454:Sulfoxides / Q000737:chemistry
chemical_list: D004852:Epoxy Compounds; D005290:Ferric Compounds; D006843:Hydrocarbons, Chlorinated; D007093:Imidazoles; D011166:Porphyrins; D013454:Sulfoxides; D006997:Hypochlorous Acid