Reaction of [RuIII(edta)(H2O)]− with H2O2 in aqueous solution. Kinetic and mechanistic investigation

Debabrata Chatterjee; Anannya Mitra; Rudi van Eldik

doi:10.1039/B617119M

Reaction of [Ru^III(edta)(H₂O)]⁻ with H₂O₂ in aqueous solution. Kinetic and mechanistic investigation†‡

Debabrata Chatterjee,*^ab Anannya Mitra^ab and Rudi van Eldik*^b

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* Corresponding authors

^a Chemistry Group, Central Mechanical Engineering Research Institute, Durgapur, India

^b Institute for Inorganic Chemistry, University of Erlangen-Nürnberg, Egerlandstrasse 1, Erlangen, Germany

Abstract

The reaction of [Ru^III(edta)(H₂O)]⁻ (1) (edta = ethylenediaminetetraacetate) with hydrogen peroxide was studied kinetically as a function of [H₂O₂], temperature (5–35 °C) and pressure (1–1300 atm) at a fixed pH of 5.1 using stopped-flow techniques. The reaction was found to consist of two steps involving the rapid formation of a [Ru^III(edta)(OOH)]²⁻ intermediate which subsequently undergoes parallel heterolytic and homolytic cleavage to produce [(edta)Ru^V [double bond, length as m-dash] O]⁻ (45%) and [(edta)Ru^IV(OH)]⁻ (55%), respectively. The water soluble trap, 2,2′-azobis(3-ethylbenzithiazoline-6-sulfonate) (ABTS), was employed to substantiate the mechanistic proposal. 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˙⁺. A detailed mechanism in agreement with the rate and activation parameters is presented, and the results are discussed with reference to data reported for the corresponding [Fe^III(edta)(H₂O)]⁻/H₂O₂ system.

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Article information

DOI: https://doi.org/10.1039/B617119M
Article type: Paper
Submitted: 22 Nov 2006
Accepted: 04 Jan 2007
First published: 30 Jan 2007

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Dalton Trans., 2007, 943-948

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Reaction of [Ru^III(edta)(H₂O)]⁻ with H₂O₂ in aqueous solution. Kinetic and mechanistic investigation

D. Chatterjee, A. Mitra and R. van Eldik, Dalton Trans., 2007, 943 DOI: 10.1039/B617119M

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