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Title: Further studies on the kinetics and mechanism of the copper-imidazole catalyzed decomposition of hydrogen peroxide

Journal Article · · J. Coord. Chem.; (United States)

The catalytic decomposition of hydrogen peroxide in the presence of the tetrakis(imidazole)copper(II) complex was investigated. The kinetics, based on the rates of oxygen evolution, indicated that a ternary copper(II)-imidazole-peroxo complex is involved in the rate-determining step. The equilibrium constant for the coordination of hydrogen peroxide to the cupric ion, and the acid dissociation constant for the coordinated H/sub 2/O/sub 2/ ligand were calculated as 1.7 M/sup /minus/1/ and 2.1 /times/ 10/sup /minus/9/ M, respectively. The ternary complex undergoes intramolecular electron transfer, with k = 4 s/sup /minus/1/, generating Cu(I) species which can react with hydrogen peroxide or dioxygen, returning to the catalytic cycle. A complete mechanism is proposed, based on the kinetics of oxygen and on the electrocatalytic behavior observed for the copper-imidazole complexes under a dioxygen atmosphere.

Research Organization:
Universidade de Sao Paulo (Brazil)
OSTI ID:
6048400
Journal Information:
J. Coord. Chem.; (United States), Vol. 18:4
Country of Publication:
United States
Language:
English