Kinetic stability of corrole complexes with manganese, copper, and zinc in environments based on acetic and sulfuric acids

Complexes of some meso- and undeca-substituted corroles with manganese, copper, and zinc are synthesized. Their stability in protolytic dissociation processes studied using spectroscopy methods increases for meso-triphenylcorrole (I) complexes in the following series of metals: Zn < Mn < Cu. The stability of copper complexes in the HOAc-H2SO4 environment increases after electron-donor substitution of molecules in the series: Cu(ms-Ph)(3)Cor (Ib) > Cu(ms-4-OCH3Ph)(3)Cor (IIb) a parts per thousand Cu(beta-Br)(8)(ms-Ph)(3)Cor (IVb) > Cu(ms-4-NO2Ph)(3)Cor (IIIb). Contrariwise, the dissociation rates of manganese corroles increase with increasing electron-donating properties of the substituents in the macrocycle: IVb < IIIb < Ia < IIa. Dissociation of metallocorroles is accompanied by donor-acceptor and acid-base interactions, as well as by intramolecular redox processes, to result in low selectivity of dissociation and formation of side products. The dissociation scheme of corrole complexes with mixed-valence d metals was proposed for the first time.