Study of acid-base interactions of mono- and diazaporphyrin indium complexes with acetic and trifluoroacetic acids by 1H NMR and electronic spectroscopy |
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Authors: | P. A. Stuzhin S. S. Ivanova I. S. Migalova |
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Affiliation: | (1) Ivanovo State University of Chemical Technology, Ivanovo, Russia |
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Abstract: | Indium complex of 13,17-dibutyl-2,3,7,8,12,18-hexamethyl-5-azaporphyrin (Cl)InMAP was synthesized, and acid-base interactions of the meso-nitrogen atoms in (Cl)InMAP and its diaza analog (Cl)InDAP with acetic and trifluoroacetic acids were studied by 1H NMR and electronic spectroscopy. Depending on the medium, the complexes and proton-donor species HA give rise to acid solvates >N(HA)n which are converted to final acid-base interaction products, H-complexes >NH+A–(HA)m or ionic associates >NH+A–(HA)l , as the acidity of the medium rises. In acetic acid solution, the acid solvates derived from more basic (Cl)InMAP exist in equilibrium with the H-associates (pKa1 = 4.45±0.03). From (Cl)InDAP, the corresponding H-associates are formed only in the presence of H2SO4 (pKa1 = 2.10±0.03). In more polar media (solutions of trifluoroacetic acid in methylene chloride), ionic associates are formed, which involve one [(Cl)InMAP, pK1 = 2.46±0.02] or two meso-nitrogen atoms [(Cl)InDAP, pK1 = 2.11±0.03, pK2 = 0.41±0.04).Translated from Zhurnal Obshchei Khimii, Vol. 74, No. 9, 2004, pp. 1546–1556.Original Russian Text Copyright © 2004 by Stuzhin, Ivanova, Migalova.This revised version was published online in April 2005 with a corrected cover date. |
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