title: Azo dye oxidation with hydrogen peroxide catalysed by manganese 1,4,7-triazacyclononane complexes in aqueous solution.
abstract: A kinetic and mechanistic study is reported of the oxidation of a number of azonaphthol dyes with hydrogen peroxide in aqueous solution, catalysed by some mono and dinuclear manganese(IV) complexes of 1,4,7-trimethyl-1,4,7-triazacyclononane (Me3TACN). The results of UV-Vis investigations, augmented by EPR and ESI-MS studies, are described for a series of experiments in which concentrations, pH and ionic strength have been varied. The reactions are characterised by an induction period followed by a relatively rapid oxidation. For the dinuclear manganese complex 2, these are consistent with an initial perhydrolysis of the manganese complex involving both the dye anion and HO2-, to give mononuclear manganese species and the operation of a catalytic cycle incorporating MnIIIL(OH)3, O = MnVL(OH)2 and MnIVL(OH)3 (L = Me3TACN) (cf. the reactions of peroxidase enzymes). ESI-MS results provide evidence for the formation and reaction (with the dye) of MnIVL(OH)3. With the mononuclear manganese complex MnIVL(OMe)3, there is a short lag-phase attributed to perhydrolysis by HO2- followed by the same catalytic cycle.
authors.affiliation: Department of Chemistry, University of York, Heslington, York, UK YO10 5DD.
authors.forename: Bruce C
authors.initials: BC
authors.lastname: Gilbert
authors.forename: John R Lindsay
authors.initials: JR
authors.lastname: Smith
authors.forename: Maurice S
authors.initials: MS
authors.lastname: Newton
authors.forename: John
authors.initials: J
authors.lastname: Oakes
authors.forename: Roger
authors.initials: R
authors.lastname: Pons i Prats