Abstract
The forms of existence and reactions of manganese(III) and copper(II) complexes with 3,7,12,18-tetramethyl-2,8,13,17-tetrabutylporphine in H2SO4, AcOH, and their mixtures of variable composition were studied. The quantitative characteristics of reversible single-electron oxidation and dissociation for the Mn(III) and Cu(II) complexes, respectively, were obtained. The formation constant of the oxidized metal porphyrin was determined for the first time. The copper(II) complex was used to devise the first kinetic scheme described satisfactorily by two kinetic equations interpreted in terms of a single mechanism of dissociation of metal porphyrins in AcOH-H2SO4 mixtures by means of two methods of accounting the equilibrium of acid dissociation of H2SO4 in acetic acid. The mechanism of the influence of alkyl substitution on the electronic structure of the coordination site in the complexes is explained.
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