From Chemistry Towards Technology Step-By-Step From Chemistry Towards Technology Step-By-Step От химии к технологии шаг за шагом 2782-1900 82484 10.52957/27821900_2022_01_113 Научные статьи Scientific articles Научные статьи The role of the entropy factor in the kinetics of complex formation of non-planar porphyrins with localized and delocalized NH bonds The role of the entropy factor in the kinetics of complex formation of non-planar porphyrins with localized and delocalized NH bonds Березин Дмитрий Борисович Berezin Dmitry Borisovich

доктор химических наук;

doctor of chemical sciences;

 Ивановский государственный химико-технологический университет Ivanovo State University of Chemistry and Technology 23 03 2022 23 03 2022 3 1 113 122 14 03 2022 22 03 2022 https://chemintech.ru/en/nauka/article/82484/view

The paper concerns NH-bonds chemical activity exhibiting in porphyrin molecules typical of macrocycles with planar or non-planar polarized struc-tures. It is not limited by the increasing rate of their metal complexing indi-cator reaction in proton-donating media in comparison with proton-donating ones. The work dwells on the entropy of the process towards more positive values as the electron-donating properties of the solvent increase. It is due to the formation of molecular complexes "porphyrin - electron-donor" increasing the solvation of the initial state of the complexing reaction. The deformation of the planar structure of the H2P macrocycle expressed by the example of N- and dodeca-substituted porphyrin accompanying by an ap-preciable polarization of the molecule does not lead to the appearance of NH-bonds chemical activity.

The paper concerns NH-bonds chemical activity exhibiting in porphyrin molecules typical of macrocycles with planar or non-planar polarized struc-tures. It is not limited by the increasing rate of their metal complexing indi-cator reaction in proton-donating media in comparison with proton-donating ones. The work dwells on the entropy of the process towards more positive values as the electron-donating properties of the solvent increase. It is due to the formation of molecular complexes "porphyrin - electron-donor" increasing the solvation of the initial state of the complexing reaction. The deformation of the planar structure of the H2P macrocycle expressed by the example of N- and dodeca-substituted porphyrin accompanying by an ap-preciable polarization of the molecule does not lead to the appearance of NH-bonds chemical activity.

 tetrapyrrole macroheterocyclic com-pounds; porphyrins; complexing reaction; chemical activity of NH bonds; activation entropy The assistance provided by Semeykin A.S., Doctor of Chemistry, Professor was greatly ap-preciated. This work was supported by Ivanovo State University of Chemistry and Technology, Ivanovo, Russia Centre for the Collective Use of Scientific Equipment (the Russian Ministry of Education and Science, Agreement No. 075-15-2021-671)

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