Mechanistic studies on oxidation of hydrogen peroxide by an oxo-bridged diiron complex in aqueous acidic media. 2008

Suranjana Das, and Jhimli Bhattacharyya, and Subrata Mukhopadhyay
Department of Chemistry, Jadavpur University, Kolkata, 700 032, India. smukhopadhyay@chemistry.jdvu.ac.in

A novel Raman spectroscopic model for the dinuclear iron site in ribonucleotide reductase and met-hemerythrin, [Fe2(micro-O)(phen)4(H2O)2]4+, 1, (phen = 1,10-phenanthroline) quantitatively oxidizes hydrogen peroxide to dioxygen via an inner-sphere electron transfer pathway. Although 1 deprotonates to form [Fe2(micro-O)(phen)4(H2O)(OH)]3+ (2) and [Fe2(micro-O)(phen)4(OH)2]2+ (3) in aqueous media, neither 2 nor 3 is reactive in oxidising H2O2. In the presence of excess phen, no phen-releasing equilibria from , and exist. Kinetic evidence of the generation of a (micro-1,2 peroxo)diiron(III,III) intermediate, prior to electron transfer, were obtained. Significant rate retardation in D2O media suggests proton coupled electron transfer (PCET) in the rate determining step of the title redox reaction.

UI MeSH Term Description Entries
D007501 Iron A metallic element with atomic symbol Fe, atomic number 26, and atomic weight 55.85. It is an essential constituent of HEMOGLOBINS; CYTOCHROMES; and IRON-BINDING PROTEINS. It plays a role in cellular redox reactions and in the transport of OXYGEN. Iron-56,Iron 56
D007700 Kinetics The rate dynamics in chemical or physical systems.
D009942 Organometallic Compounds A class of compounds of the type R-M, where a C atom is joined directly to any other element except H, C, N, O, F, Cl, Br, I, or At. (Grant & Hackh's Chemical Dictionary, 5th ed) Metallo-Organic Compound,Metallo-Organic Compounds,Metalloorganic Compound,Organometallic Compound,Metalloorganic Compounds,Compound, Metallo-Organic,Compound, Metalloorganic,Compound, Organometallic,Compounds, Metallo-Organic,Compounds, Metalloorganic,Compounds, Organometallic,Metallo Organic Compound,Metallo Organic Compounds
D004579 Electron Transport The process by which ELECTRONS are transported from a reduced substrate to molecular OXYGEN. (From Bennington, Saunders Dictionary and Encyclopedia of Laboratory Medicine and Technology, 1984, p270) Respiratory Chain,Chain, Respiratory,Chains, Respiratory,Respiratory Chains,Transport, Electron
D006861 Hydrogen Peroxide A strong oxidizing agent used in aqueous solution as a ripening agent, bleach, and topical anti-infective. It is relatively unstable and solutions deteriorate over time unless stabilized by the addition of acetanilide or similar organic materials. Hydrogen Peroxide (H2O2),Hydroperoxide,Oxydol,Perhydrol,Superoxol,Peroxide, Hydrogen
D006863 Hydrogen-Ion Concentration The normality of a solution with respect to HYDROGEN ions; H+. It is related to acidity measurements in most cases by pH pH,Concentration, Hydrogen-Ion,Concentrations, Hydrogen-Ion,Hydrogen Ion Concentration,Hydrogen-Ion Concentrations
D013057 Spectrum Analysis The measurement of the amplitude of the components of a complex waveform throughout the frequency range of the waveform. (McGraw-Hill Dictionary of Scientific and Technical Terms, 6th ed) Spectroscopy,Analysis, Spectrum,Spectrometry
D014867 Water A clear, odorless, tasteless liquid that is essential for most animal and plant life and is an excellent solvent for many substances. The chemical formula is hydrogen oxide (H2O). (McGraw-Hill Dictionary of Scientific and Technical Terms, 4th ed) Hydrogen Oxide

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