Modification of Tetraphenylporphyrin Ring in Manganese(III) Complexes-Theoretical Description of the Influence on Their Physicochemical Properties

摘要

Metalloporphyrins are known to be efficient catalysts in oxidation of hydrocarbons. To understand a mechanism of oxidation processes detailed knowledge of the electronic and structural parameters of these systems is required. Here, atomic parameters calculated by means of DFT method for the selected manganese porphyrins are correlated with experimental redox potential. The results of calculations carried out for systems with modification in phenyl substituents showed that charge of porphyrin ring and charge of axial ligand are good theoretical descriptors of effect introduced by the substituent. These descriptors correlate (R~2=0.97) with experimental value of redox potential of the Mn~(III)/Mn~(II) system.