title: Kinetics and mechanism of the reaction of [RuIII(edta)(H2O)]- with HOBr to form an intermediate RuV=O complex in aqueous solution.
abstract: The interaction of [Ru(III)(edta)(H(2)O)](-) (1) (edta = ethylenediaminetetraacetate) with the oxygen transfer agent HOBr, was studied kinetically as a function of [HOBr] and temperature (5-35 degrees C) at a fixed pH of 6.2. Spectroscopic evidence is reported for the formation of a high valent intermediate (edta)Ru(V)=O complex. Water soluble 2,2'-azobis(3-ethylbenzithiazoline-6-sulfonate) (ABTS) was employed as a trap for this intermediate in order to gain further mechanistic information. Reactions were carried out under pseudo-first conditions for [ABTS] >> [HOBr] >> [1], and were monitored as a function of time for the formation of the one-electron oxidation product ABTS(*+). The reported kinetic data are interpreted in terms of a suggested reaction mechanism and discussed in reference to data reported before.
authors.affiliation: Chemistry Group, Central Mechanical Engineering Research Institute, Durgapur, 713209, India.
authors.forename: Debabrata
authors.initials: D
authors.lastname: Chatterjee
authors.forename: Anannya
authors.initials: A
authors.lastname: Mitra
authors.forename: Rudi
authors.initials: R
authors.lastname: van Eldik
mesh_terms: D001959:Bromates / Q000737:chemistry*; D004492:Edetic Acid; D007700:Kinetics; D009942:Organometallic Compounds / Q000737:chemistry*; D012428:Ruthenium / Q000737:chemistry*; D012995:Solubility; D013057:Spectrum Analysis; D013696:Temperature
chemical_list: D001959:Bromates; D009942:Organometallic Compounds; D012428:Ruthenium; D004492:Edetic Acid; C027664:hypobromous acid