title: Verdoheme reactivity. Remarkable paramagnetically shifted (1)H NMR spectra of intermediates from the addition of hydroxide or methoxide with Fe(II) and Fe(III) verdohemes.
abstract: Studies of the reaction of 5-oxaporphyrin iron complexes (verdohemes) with methoxide ion or hydroxide ion have been undertaken to understand the initial step of ring opening of verdohemes. High-spin [ClFe(III)(OEOP)] undergoes a complex series of reactions upon treatment with hydroxide ion in chloroform, and similar species are also detected in dichloromethane, acetonitrile, and dimethyl sulfoxide. Three distinct paramagnetic intermediates have been identified by (1)H NMR spectroscopy. These reactive species are formed by addition of hydroxide to the macrocycle and to the iron as an axial ligand. Treatment of low-spin [(py)(2)Fe(II)(OEOP)]Cl (OEOP is the monoanion of octaethyl-5-oxaporphyrin) with excess methoxide ion in pyridine solution produces [(py)(n)()Fe(II)(OEBOMe)] (n = 1 or 2) ((OEBOMe), dianion of octaethylmethoxybiliverdin), whose (1)H NMR spectrum undergoes marked alteration upon addition of further amounts of methoxide ion. An identical (1)H NMR spectrum, which is characterized by methylene resonances with both upfield and downfield paramagnetic shifts, is formed upon treatment of [Fe(II)(OEBOMe)](2) with methoxide in pyridine solution and results from the formation of [(MeO)Fe(II)(OEBOMe)](-).
authors.affiliation: Department of Chemistry, University of California, Davis, California 95616, USA.
authors.forename: L
authors.initials: L
authors.lastname: Latos-Grazyński
authors.forename: J
authors.initials: J
authors.lastname: Wojaczyński
authors.forename: R
authors.initials: R
authors.lastname: Koerner
authors.forename: J J
authors.initials: JJ
authors.lastname: Johnson
authors.forename: A L
authors.initials: AL
authors.lastname: Balch
mesh_terms: D000097:Acetonitriles / Q000737:chemistry; D004121:Dimethyl Sulfoxide / Q000737:chemistry; D005290:Ferric Compounds / Q000737:chemistry*; D005296:Ferrous Compounds / Q000737:chemistry*; D006418:Heme / Q000031:analogs & derivatives* / Q000737:chemistry*; D006859:Hydrogen; D006878:Hydroxides / Q000737:chemistry*; D009682:Magnetic Resonance Spectroscopy / Q000379:methods; D000432:Methanol / Q000737:chemistry*; D008752:Methylene Chloride / Q000737:chemistry; D008958:Models, Molecular; D008968:Molecular Conformation
chemical_list: D000097:Acetonitriles; D005290:Ferric Compounds; D005296:Ferrous Compounds; D006878:Hydroxides; C099547:verdoheme; D006418:Heme; D008752:Methylene Chloride; D006859:Hydrogen; D000432:Methanol; D004121:Dimethyl Sulfoxide; C032159:acetonitrile