title: O2 reduction by a functional heme/nonheme bis-iron NOR model complex.
abstract: O(2) reactivity of a functional NOR model is investigated by using electrochemistry and spectroscopy. The electrochemical measurements using interdigitated electrodes show very high selectivity for 4e O(2) reduction with minimal production of partially reduced oxygen species (PROS) under both fast and slow electron flux. Intermediates trapped at cryogenic temperatures and characterized by using resonance Raman spectroscopy under single-turnover conditions indicate that an initial bridging peroxide intermediate undergoes homolytic O--O bond cleavage generating a trans heme/nonheme bis-ferryl intermediate. This bis ferryl species can oxygenate 2 equivalents of a reactive substrate.
authors.affiliation: Department of Chemistry, Stanford University, Stanford, CA 94305, USA. jpc@stanford.edu
authors.forename: James P
authors.initials: JP
authors.lastname: Collman
authors.forename: Abhishek
authors.initials: A
authors.lastname: Dey
authors.forename: Ying
authors.initials: Y
authors.lastname: Yang
authors.forename: Somdatta
authors.initials: S
authors.lastname: Ghosh
authors.forename: Richard A
authors.initials: RA
authors.lastname: Decréau
mesh_terms: D002384:Catalysis; D020134:Catalytic Domain; D020372:Dexfenfluramine; D004563:Electrochemistry; D003576:Electron Transport Complex IV / Q000737:chemistry / Q000378:metabolism; D005290:Ferric Compounds / Q000737:chemistry; D005296:Ferrous Compounds / Q000737:chemistry; D006418:Heme / Q000737:chemistry*; D006861:Hydrogen Peroxide / Q000737:chemistry / Q000378:metabolism; D007501:Iron / Q000737:chemistry*; D007700:Kinetics; D008956:Models, Chemical; D008958:Models, Molecular; D015394:Molecular Structure; D010088:Oxidoreductases / Q000737:chemistry* / Q000378:metabolism; D010100:Oxygen / Q000737:chemistry* / Q000378:metabolism; D010545:Peroxides / Q000737:chemistry / Q000378:metabolism; D013059:Spectrum Analysis, Raman
chemical_list: D005290:Ferric Compounds; D005296:Ferrous Compounds; D010545:Peroxides; D006418:Heme; D006861:Hydrogen Peroxide; D007501:Iron; D020372:Dexfenfluramine; D010088:Oxidoreductases; C034747:nitric-oxide reductase; D003576:Electron Transport Complex IV; D010100:Oxygen