Remarkably high catalytic activity of the Ru(III)(edta)/H2O2 system towards degradation of the azo-dye Orange II.

The Ru(III)(edta)/H(2)O(2) system (edta(4-) = ethylenediaminetretaacetate) was found to degrade the azo-dye Orange II at remarkably high efficiency under ambient conditions. Catalytic degradation of the dye was studied by using rapid-scan spectrophotometry as a function of [H(2)O(2)], [Orange II] and pH. Spectral analyses and kinetic data point towards a catalytic pathway involving the rapid formation of [Ru(III)(edta)(OOH)](2-) followed by the immediate subsequent degradation of Orange II prior to the conversion of [Ru(III)(edta)(OOH)](2-) to [Ru(IV)(edta)(OH)](-) and [Ru(V)(edta)(O)](-)via homolysis and heterolysis of the O-O bond, respectively. The higher oxidation state Ru(IV) and Ru(V) complexes react three orders of magnitude slower with Orange II than the Ru(III)-hydroperoxo complex. In comparison to biological oxygen transfer reactions, the Ru(edta) complexes show the reactivity order Compound 0 ≫ Compounds I and II.

[1]  R. Eldik,et al.  MnII―A fascinating oxidation catalyst: Mechanistic insight into the catalyzed oxidative degradation of organic dyes by H2O2 , 2010 .

[2]  R. van Eldik,et al.  Comparative study of the catalytic activity of [Mn(II)(bpy)2Cl2] and [Mn2(III/IV)(mu-O)2(bpy)4](ClO4)3 in the H2O2 induced oxidation of organic dyes in carbonate buffered aqueous solution. , 2010, Dalton transactions.

[3]  R. van Eldik,et al.  Direct comparison of the reactivity of model complexes for Compounds 0, I, and II in oxygenation, hydrogen-abstraction, and hydride-transfer processes. , 2009, Chemistry.

[4]  R. Eldik,et al.  Metal ion-catalyzed oxidative degradation of Orange II by H2O2. High catalytic activity of simple manganese salts , 2009 .

[5]  R. van Eldik,et al.  Which oxidant is really responsible for P450 model oxygenation reactions? A kinetic approach. , 2008, Angewandte Chemie.

[6]  D. Chatterjee,et al.  Reaction of [RuIII(edta)(H2O)]- with H2O2 in aqueous solution. Kinetic and mechanistic investigation. , 2007, Dalton transactions.

[7]  R. van Eldik,et al.  Further mechanistic information on the reaction between FeIII(edta) and hydrogen peroxide: observation of a second reaction step and importance of pH. , 2004, Inorganic chemistry.

[8]  A. Wheatley,et al.  The toxicity of textile reactive azo dyes after hydrolysis and decolourisation. , 2003, Journal of biotechnology.

[9]  G. Peschek,et al.  Catalase-peroxidase from synechocystis is capable of chlorination and bromination reactions. , 2001, Biochemical and biophysical research communications.

[10]  C. Bauer,et al.  Investigation of the interaction between a sulfonated azo dye (AO7) and a TiO2 surface , 1999 .

[11]  D. Chatterjee Properties and reactivities of polyaminopolycarboxylate (pac) complexes of ruthenium , 1998 .

[12]  A. Oroskar,et al.  Effects of hydroxyl radical scavengers on relaxation of supercoiled DNA by aminomethyl-trimethyl-psoralen and monochromatic UVA photons. , 1996, Free radical biology & medicine.

[13]  C. Winterbourn Toxicity of iron and hydrogen peroxide: the Fenton reaction. , 1995, Toxicology letters.

[14]  Amitava Das,et al.  Synthesis, kinetics, and physicochemical studies of a new mixed-valent heterobinuclear cyano-bridged ruthenium(III)-iron(II) complex , 1993 .

[15]  R. Shepherd Reconsidered mechanism in RuIII(hedta)-catalyzed epoxidation of stilbenes , 1993 .

[16]  Mark A. Brown,et al.  Predicting azo dye toxicity , 1993 .

[17]  H. C. Bajaj,et al.  Kinetics and mechanism of the ligand substitution reactions of ethylenediaminetetraacetate complexes of ruthenium(III) in aqueous solution , 1988 .

[18]  A. Diamantis,et al.  Preparation and structure of ethylenediaminetetraacetate complexes of ruthenium(II) with dinitrogen, carbon monoxide, and other .pi.-acceptor ligands , 1981 .

[19]  C. Creutz,et al.  Properties and reactivities of pentadentate ethylenediaminetetraacetate complexes of ruthenium(III) and -(II) , 1979 .