Abstract

Thermodynamic equilibrium constants of protonation of (acetato)(octakis)(4-tert-butylphenyl)- and (acetato)(octakis(3-trifluoromethylphenyl)tetraazaporphynato)manganese(III) in a trifluoroacetic acid–dichloromethane medium are determined via spectrophotometric titration using Hammett acidity function H₀ for a mixed solvent. The effect of the higher basicity of the mono-protonated forms against that of the neutral forms is established and interpreted using literature data on tetraazaporphyrin analogs. The role of functional substitution and the electronic structure of coordination centers in the acid–base behavior of porphyrazine complexes is determined. The obtained data are important for developing the theory of reactivity of macroheterocyclic compounds and creating actual supramolecular 2D and 3D structures based on porphyrazines.

中文翻译：

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高取代锰四氮杂的热力学碱度常数及其与分子结构的联系

摘要

三氟乙酸-二氯甲烷介质中（乙酰基）（octakis）（4-叔丁基苯基）-和（乙酰基）（octakis（3-三氟甲基苯基）四氮杂卟啉）锰（III）质子化的热力学平衡常数通过分光光度法滴定确定哈米特酸度函数H ₀为混合溶剂。使用关于四氮杂卟啉类似物的文献数据建立并解释了单质子化形式的较高碱度对中性形式的影响。确定了功能取代和配位中心电子结构在四氮杂卟啉配合物的酸碱行为中的作用。获得的数据对于开发大杂环化合物的反应性理论和创建基于四氮杂卟啉的实际超分子 2D 和 3D 结构非常重要。