title: Kinetics and mechanism of O-O bond cleavage in the reaction of [RuIII(edta)(H2O)]- with hydroperoxides in aqueous solution.
abstract: The reactions of [Ru(III)(edta)(H(2)O)](-) (1) (edta = ethylenediaminetetraacetate) with tert-butylhydroperoxide ((t)BuOOH) and potassium hydrogenpersulfate (KHSO(5)) were studied kinetically as a function of oxidant concentration and temperature (10-30 degrees C) at a fixed pH of 6.1 using stopped-flow techniques. Kinetic results were analyzed by using global kinetic analysis techniques. The reaction was found to consist of two steps involving the rapid formation of a [Ru(III)(edta)(OOR)](2-) intermediate, which subsequently undergoes heterolytic cleavage to form [(edta)Ru(V)=O](-). Since [(edta)Ru(V)=O](-) was produced almost quantitatively in the reaction of 1 with the hydroperoxides (t)BuOOH and KHSO(5), the common mechanism is one of heterolytic scission of the O-O bond. The water soluble and easy to oxidize substrate 2,2'-azobis(3-ethylbenzithiazoline-6-sulfonate (ABTS), was employed to substantiate the mechanistic proposal. Reactions were carried out under pseudo-first order conditions for [ABTS] >> [hydroperoxide] >> [1], and were monitored as a function of time for the formation of the one-electron oxidation product ABTS (*+). The detailed suggested mechanism is consistent with the reported rate and activation parameters, and discussed in reference to the results reported for the reaction of [Ru(II)(edta)(H(2)O)](-) with H(2)O(2).
authors.affiliation: Chemistry Group, Central Mechanical Engineering Research Institute, Durgapur, 713209, India.
authors.forename: Debabrata
authors.initials: D
authors.lastname: Chatterjee
authors.forename: Anindita
authors.initials: A
authors.lastname: Sikdar
authors.forename: Vidya R
authors.initials: VR
authors.lastname: Patnam
authors.forename: Alexander
authors.initials: A
authors.lastname: Theodoridis
authors.forename: Rudi
authors.initials: R
authors.lastname: van Eldik
mesh_terms: D004492:Edetic Acid / Q000737:chemistry*; D004583:Electrons; D006861:Hydrogen Peroxide / Q000737:chemistry*; D006863:Hydrogen-Ion Concentration; D007700:Kinetics; D008956:Models, Chemical; D009942:Organometallic Compounds / Q000737:chemistry*; D010084:Oxidation-Reduction; D010100:Oxygen / Q000737:chemistry*; D012428:Ruthenium / Q000737:chemistry*; D012996:Solutions / Q000737:chemistry; D013056:Spectrophotometry, Ultraviolet; D014867:Water / Q000737:chemistry*
chemical_list: D009942:Organometallic Compounds; D012996:Solutions; D014867:Water; D012428:Ruthenium; D004492:Edetic Acid; D006861:Hydrogen Peroxide; D010100:Oxygen