Extremely Electron-Poor Bis(diarylmethylium)-Substituted Ferrocenes and the First Peroxoferrocenophane

Larissa A. Casper; Steffen O?wald; Patrick Anders; Lisa-Catherine Rosenbaum; Rainer F. Winter

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Extremely Electron-Poor Bis(diarylmethylium)-Substituted Ferrocenes and the First Peroxoferrocenophane

机译：极差的双（二芳基甲基） - 取出的甲烷酮和第一个过氧氧键体

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摘要

We have prepared and studied extremely electron-poor, deeply colored dicationic 1,1'-bis(diarylmethylium)-substituted ferrocenes [(η5-C_5H_4-CAr_2)_2Fe]~(2+) with various aryl substituents as their [B{C_6H_3(CF_3)_2-3,5}_4]- salts. Due to the strong acceptor substitution, the redox potential for the ferrocene-based oxidation of the anisyl- or 2-methylanisyl-substituted congeners 1b~(2+) and 1c~(2+) is close to or even surpasses that of the second oxidation of parent ferrocene, i.e. the Cp_2Fe~(+/2+) couple. The strongly Lewis-acidic character of these complexes is manifest through strong interactions with donor solvents, which lead to a significant reduction of the intensities of the chargetransfer bands in their electronic spectra and to solvatochromism. The reduced forms of the complexes tend to dimerize or oligomerize as revealed by EPR spectroscopy. Direduced 1b selectively reacts with molecular oxygen to form a peroxo-bis(diarylmethyl)[4]ferrocenophane, which was also characterized by X-ray crystallography.

机译：我们制备并研究了以各种芳基取代基为[B{C_6H_3（CF_3）_2-3,5}u 4]盐的极贫电子、深有色的二茂铁[（η5-C_5H_4-CAr_2）_2Fe]~（2+）。由于强烈的受体取代，苯甲酰基或2-甲基苯甲酰基取代的同系物1b~（2+）和1c~（2+）的二茂铁基氧化的氧化还原电位接近甚至超过母体二茂铁的第二次氧化，即Cp_2Fe~（+/2+）偶。这些配合物的强路易斯酸性特征通过与施主溶剂的强相互作用得以体现，这导致它们的电子光谱中电荷转移带的强度显著降低，并导致溶剂化变色。EPR光谱显示，复合物的还原形式倾向于二聚或齐聚。Direduced 1b选择性地与分子氧反应，形成过氧双（二芳基甲基）[4]二茂铁，这也通过X射线晶体学进行了表征。

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《Zeitschrift fur Anorganische und Allgemeine Chemie》 |2020年第13期|共14页
作者
Larissa A. Casper; Steffen O?wald; Patrick Anders; Lisa-Catherine Rosenbaum; Rainer F. Winter;
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作者单位

Fachbereich Chemie Universit?t Konstanz Universit?tsstra?e 10 78453 Konstanz Germany;

Fachbereich Chemie Universit?t Konstanz Universit?tsstra?e 10 78453 Konstanz Germany;

Fachbereich Chemie Universit?t Konstanz Universit?tsstra?e 10 78453 Konstanz Germany;

Fachbereich Chemie Universit?t Konstanz Universit?tsstra?e 10 78453 Konstanz Germany;

Fachbereich Chemie Universit?t Konstanz Universit?tsstra?e 10 78453 Konstanz Germany;

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正文语种 eng
中图分类化学;
关键词
Ferrocene; Tritylium; Electrochemistry; Spectroelectrochemistry; Ferrocenophane; Peroxo compound; EPR spectroscopy; Solvatochromism;

机译：铁茂;TRITYLIUM;电化学;光谱电化学;亚罗氧氧氧烷;过氧化合物;EPR光谱;溶溶度;

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Extremely Electron-Poor Bis(diarylmethylium)-Substituted Ferrocenes and the First Peroxoferrocenophane

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