Abstract
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.
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Original Russian Text © S.G. Pukhovskaya, Dao Tkhe Nam, Chan Ding Fien, E.N. Domanina, Yu.B. Ivanova, A.S. Semeikin, 2017, published in Zhurnal Fizicheskoi Khimii, 2017, Vol. 91, No. 9, pp. 1508–1519.
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Pukhovskaya, S.G., Nam, D.T., Fien, C.D. et al. Acid–base and coordination properties of Meso-substituted porphyrins in nonaqueous solutions. Russ. J. Phys. Chem. 91, 1692–1702 (2017). https://doi.org/10.1134/S0036024417090242
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DOI: https://doi.org/10.1134/S0036024417090242