Abstract

The kinetics of redox isomerization of ferrocenylcarbenium ions obtained via protonation of ferrocene derivatives with perchloric acid in dioxane has been studied by means of electron absorption spectroscopy method from accumulation of ferrocenium cations. It has been shown that the dependences of the rate of ferrocenium cations accumulation on the components concentration is extremal in certain cases and is determined by the nature of metal complex and the initial ratio of the metal complex and acid. Stabilization of carbocations via their solvation with acetonitrile, DMF, and DMSO as well as via coordination with the starting compound leads to partial or complete loss of their ability to redox isomerization. Schemes of the metal complexes protonation and results of their kinetic analysis confirming the obtained concentration dependencies are given.

中文翻译：

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二茂铁衍生物与强酸的质子化。二茂铁基碳鎓离子的氧化还原异构现象的动力学关系

摘要

通过电子吸收光谱法研究了二茂铁鎓阳离子的积累，研究了二茂铁衍生物与高氯酸在二恶烷中的质子化作用所得到的二茂铁基碳鎓离子的氧化还原异构化动力学。已经表明，在某些情况下，二茂铁阳离子积累速率对组分浓度的依赖性极高，并且取决于金属络合物的性质以及金属络合物与酸的初始比例。碳阳离子通过与乙腈，DMF和DMSO的溶剂化以及与起始化合物的配位而稳定，导致其氧化还原异构化的能力部分或全部丧失。