名称:
Role of the central manganese(III) ion in the hydrogen peroxide oxidation mechanism of (2,3,7,8,12,13,17,18-octaalkyl-5(5,10)(5,15)-phenyl(diphenyl)porphinato)chloromanganese(III)
摘要:
Complete kinetic description and spectral manifestation of the hydrogen peroxide oxidation of (2,3,7,8,12,13,17,18-octamethyl- and (2,3,7,8,12,13,17,18-octaethyl-5-phenylporphinato)chloromanganese(III), (2,3,7,8,12,13,17,18-octaethyl-5,10-diphenyl- and (2,3,7,8,12,13,17,18-octaethyl-5,15-diphenylporphinato)chloromanganese(III) complexes in water-organic solutions are presented. Two H2O2 concentration ranges with different reaction mechanisms and products were distinguished. The ion-molecular oxidation mechanism was substantiated and the key role of coordination of various hydrogen peroxide species, their activation, oxidation and reduction was demonstrated. Multiple substitution in the coordinated macrocycle was found to change the electronic state of the coordination site and quantitative characteristics of the oxidation; this can be used to develop the synthetic models of natural oxide reductases.