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Mechanism of catalase activity in aqueous solutions of dimanganese(III,IV) ethylenediamine-N,N prime -diacetate

Journal Article · · Inorganic Chemistry; (USA)
DOI:https://doi.org/10.1021/ic00330a003· OSTI ID:6956688
;  [1]
  1. Louisiana State Univ., Baton Rouge (USA)
Manganous ions, ligated by ethylenediamine-N,N{prime}-diacetate (edda = L) decompose hydrogen peroxide with a rate law {minus}d(H{sub 2}O{sub 2})/dt = k{sub 17}(Mn(edda))(H{sub 2}O{sub 2}) where k{sub 17} = 5.4 M{sup {minus}1} s{sup {minus}1} at pH 7. The reduction of peroxide to water is initiated by the reaction of Mn{sup II}L with a dinuclear Mn{sup III,IV}L{sub 2}. A subsequent fast reaction between the transient product of this reaction and hydrogen peroxide or tert-butyl hydroperoxide effectively oxidizes Mn(II) to Mn(IV) in a concerted step without formation of the hydroxyl radical. The green mixed-valence complex, which is probably a bis({mu}-oxo)-bridged structure, is stable in neutral aqueous solution and exhibits a 16-line ESR signal in frozen solution. The basis of catalase activity is the autocatalytic formation of this complex when hydrogen peroxide is reduced by manganese(II). The catalase cycle is independent of the formation of oxy radicals. Mononuclear Mn{sup III}edda and Mn{sup II}edda react with superoxide radicals, but the decomposition of peroxide is virtually independent of these reactions. In unbuffered solutions, with a moderate excess of hydrogen peroxide, an oscillation in the concentration of the dinuclear complex is detected. 28 refs., 10 figs., 5 tabs.
OSTI ID:
6956688
Journal Information:
Inorganic Chemistry; (USA), Journal Name: Inorganic Chemistry; (USA) Vol. 29:5; ISSN 0020-1669; ISSN INOCA
Country of Publication:
United States
Language:
English