Kinetics and mechanism of the reaction of [RuIII(edta)(H2O)]- with HOBr to form an intermediate RuV=O complex in aqueous solution

Dalton Trans. 2006 Oct 21:(39):4691-5. doi: 10.1039/b604473e. Epub 2006 Aug 3.

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.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Bromates / chemistry*
  • Edetic Acid
  • Kinetics
  • Organometallic Compounds / chemistry*
  • Ruthenium / chemistry*
  • Solubility
  • Spectrum Analysis
  • Temperature

Substances

  • Bromates
  • Organometallic Compounds
  • Ruthenium
  • Edetic Acid
  • hypobromous acid