title: Conflicting Role of Water in the Activation of H2O2 and the Formation and Reactivity of Non-Heme Fe(III)-OOH and Fe(III)-O-Fe(III) Complexes at Room Temperature.
abstract: The formation of an Fe(III)-OOH species by reaction of complex 1 ([(MeN3Py)Fe(II)(CH3CN)2](2+)) with H2O2 at room temperature is reported and is studied by a combination of UV/vis absorption, EPR, and resonance Raman spectroscopies. The formation of the Fe(III)-OOH species, and its subsequent conversion to relatively inert Fe(III)-O-Fe(III) species, is shown to be highly dependent on the concentration of water, with excess water favoring the formation of the latter species, which is studied by UV/vis absorption spectroelectrochemistry also. The presence of acetic acid increases the rate and extent of oxidation of 1 to its iron(III) state and inhibits the wasteful decomposition of H2O2 but does not affect significantly the spectroscopic properties of the Fe(III)-OOH species formed.
authors.affiliation: Molecular Inorganic Chemistry, Stratingh Institute for Chemistry, Faculty of Mathematics and Natural Sciences, University of Groningen , Nijenborgh 4, 9747AG, Groningen, The Netherlands.
authors.forename: Sandeep K
authors.initials: SK
authors.lastname: Padamati
authors.affiliation: Molecular Inorganic Chemistry, Stratingh Institute for Chemistry, Faculty of Mathematics and Natural Sciences, University of Groningen , Nijenborgh 4, 9747AG, Groningen, The Netherlands.
authors.forename: Apparao
authors.initials: A
authors.lastname: Draksharapu
authors.affiliation: Molecular Inorganic Chemistry, Stratingh Institute for Chemistry, Faculty of Mathematics and Natural Sciences, University of Groningen , Nijenborgh 4, 9747AG, Groningen, The Netherlands.
authors.forename: Duenpen
authors.initials: D
authors.lastname: Unjaroen
authors.affiliation: Molecular Inorganic Chemistry, Stratingh Institute for Chemistry, Faculty of Mathematics and Natural Sciences, University of Groningen , Nijenborgh 4, 9747AG, Groningen, The Netherlands.
authors.forename: Wesley R
authors.initials: WR
authors.lastname: Browne
mesh_terms: D019342:Acetic Acid / Q000737:chemistry; D000097:Acetonitriles / Q000737:chemistry; D000475:Alkenes / Q000737:chemistry; D056831:Coordination Complexes / Q000737:chemistry*; D055664:Electrochemical Techniques; D006861:Hydrogen Peroxide / Q000737:chemistry*; D058085:Iron Compounds / Q000737:chemistry*; D007700:Kinetics; D008024:Ligands; D010084:Oxidation-Reduction; D013696:Temperature; D014867:Water / Q000737:chemistry*
chemical_list: D000097:Acetonitriles; D000475:Alkenes; D056831:Coordination Complexes; D058085:Iron Compounds; D008024:Ligands; D014867:Water; D006861:Hydrogen Peroxide; D019342:Acetic Acid; C032159:acetonitrile