title: Oxidative verdoheme formation and stabilization by axial isocyanide ligation.
abstract: The effect of isocyanides as axial ligands on the formation and stability of verdoheme by oxidation has been examined. The reaction of [Fe(III)(OEPO)]2 with t-butyl isocyanide under dioxygen-free conditions results in the formation of (t-BuNC)2Fe(II)(OEPO*) with an electron paramagnetic resonance at g=2.009 with a peak-to-peak separation of 23.5 G at 4 K. (OEPO is the trianion of octaethyloxophlorin and OEPO* is the radical dianion obtained from OEPO by one-electron oxidation.) Exposure of chloroform solutions of either (2,6-xylylNC)2Fe(II)(OEPO*) or (t-BuNC)2Fe(II)(OEPO*) to dioxygen followed by the addition of ammonium hexafluorophosphate results in their transformation into the diamagnetic verdohemes, [(2,6-xylylNC)2Fe(II)(OEOP)](PF6) and [(t-BuNC)2Fe(II)(OEOP)](PF6), yields 68 and 70%, respectively. (OEOP is the anion of octaethyl-5-oxaporphyrin.) The oxidation reactions of (2,6-xylylNC)2Fe(II)(OEPO*) and (t-BuNC)2Fe(II)(OEPO*) have also been monitored by 1H NMR spectroscopy. No resonances due to paramagnetic products could be detected, the reactions appear to result only in the formation of the diamagnetic verdohemes, and the products are not susceptible to further oxidation.
authors.affiliation: Department of Chemistry, University of California at Davis, One Shields Avenue, Davis, California 95616, USA.
authors.forename: Sankar Prasad
authors.initials: SP
authors.lastname: Rath
authors.forename: Marilyn M
authors.initials: MM
authors.lastname: Olmstead
authors.forename: Alan L
authors.initials: AL
authors.lastname: Balch
mesh_terms: D018360:Crystallography, X-Ray; D003486:Cyanides / Q000737:chemistry; D005290:Ferric Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D005296:Ferrous Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D006418:Heme / Q000031:analogs & derivatives* / Q000737:chemistry*; D009682:Magnetic Resonance Spectroscopy; D008958:Models, Molecular; D008968:Molecular Conformation; D015394:Molecular Structure; D010084:Oxidation-Reduction
chemical_list: D003486:Cyanides; D005290:Ferric Compounds; D005296:Ferrous Compounds; C099547:verdoheme; D006418:Heme