Abstract

Mn(III)-5-(4-nitrophenyl)-10,15,20-triphenylporphyrin and Mn(III)-5,10,15-tri(4-nitrophenyl)-20-phenylporphyrin were synthesized by complex formation reactions of the specified porphyrins and by metal exchange of Cd porphyrin complexes with MnCl₂ in dimethylformamide. The products were identified by mass spectrometry and UV-Vis, IR, and ¹H NMR spectroscopy. Partial reduction of Mn(III) to Mn(II) takes place upon dissolution of manganese(III) complexes in DMF. The addition of solid NaOH to a solution in DMF or ethanolamine gives unstable Mn(II) porphyrins. The photochemical stability and oxidative degradation of Mn(III) porphyrins were studied in chloroform and in a chloroform–hydrogen peroxide mixture. The metal exchange reaction between asymmetrically substituted Cd(II) porphyrins and MnCl₂ in DMF was studied. The kinetic parameters of the reaction were calculated. The influence of substituents and the nature of the salt on the kinetic parameters of the metal exchange reaction was identified.

中文翻译：

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不对称取代Mn(III)-硝基苯基卟啉的合成及性能

摘要

通过络合反应合成了Mn(III)-5-(4-硝基苯基)-10,15,20-三苯基卟啉和Mn(III)-5,10,15-三(4-硝基苯基)-20-苯基卟啉指定的卟啉并通过在二甲基甲酰胺中用 MnCl ₂进行 Cd 卟啉配合物的金属交换。通过质谱、UV-Vis、IR 和¹ H NMR 光谱鉴定产物。当锰(III)络合物溶解在DMF中时，Mn(III)部分还原为Mn(II)。将固体 NaOH 添加到 DMF 或乙醇胺溶液中会产生不稳定的 Mn(II) 卟啉。在氯仿和氯仿-过氧化氢混合物中研究了锰（III）卟啉的光化学稳定性和氧化降解。研究了不对称取代的Cd(II)卟啉与MnCl ₂在DMF中的金属交换反应。计算了反应的动力学参数。确定了取代基和盐的性质对金属交换反应动力学参数的影响。