Acid–base and coordination properties of Meso-substituted porphyrins in nonaqueous solutions

详细

Acid–base and coordination properties of alkyl and aryl meso-substituted porphyrins are studied spectrophotometrically in nonaqueous solutions. It is found that the nature of the substituent greatly affects the basicity of ligands for porphyrins characterized by a flat structure of macrocycle. The electronic effects of substituents have a much weaker influence on the kinetics of complexing. These effects could be due to the opposite orientation of some factors: an increase in the basicity and stability of the N–H bonds of porphyrin reaction centers. Dissociation constants pK_b of the cationic forms of meso-substituted derivatives of porphyrin are measured. The values of pK_b are in good agreement with classic concepts of the nature of substituents, particularly those indirectly included in the macrocycle through phenyl buffer rings.