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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >Remarkable isolation,structural characterisation and electrochemistry of unexpected scrambling analogues of 5-ferrocenyl-10,20-diphenylporphyrin
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Remarkable isolation,structural characterisation and electrochemistry of unexpected scrambling analogues of 5-ferrocenyl-10,20-diphenylporphyrin

机译：5-二茂铁基-10,20-二苯基卟啉的意想不到的加扰类似物的显着分离，结构表征和电化学

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摘要

Selective condensation of 5-ferrocenyldipyrromethane,1,and dipyrromethane,2,with benzaldehyde,3,led to 5-ferrocenyl-10,20-diphenylporphyrin,5.During the condensation,an unusually large amount of scrambling was observed which led to the isolation of two further ferrocenylated porphyrin analogues 6 and 7.The structure of 6 was confirmed by a single-crystal X-ray study.A mechanism is proposed for this atypical scrambling which is likely to involve acid-catalysed reversion of the dipyrromethane synthesis.~1H NMR further elucidated the structures of each complex and showed the existence of atropisomerism.An electrochemical study(cyclic voltammetry,Osteryoung square wave and linear sweep voltammetry)showed that there exists a linear relationship between the sum of the group electronegativities of meso substituents of the obtained porphyrins and the formal reduction potentials of the two observed ring-centred reduction processes,the meso substituent ferrocenyl-based oxidation process and the first ring-centred oxidation wave.These four relationships could be mathematically quantified.Due to the strong electron-withdrawing properties of the oxidised ferrocenium group,the second ring centred oxidation wave fell outside the potential window of dichloromethane as solvent.
机译：5-二茂铁基二吡咯甲烷1和二吡咯甲烷2与苯甲醛3选择性缩合为5-二茂铁基-10,20-二苯基卟啉5.在缩合过程中，观察到异常大量的加扰，导致分离的两个另外的二茂铁化的卟啉类似物6和7.通过单晶X射线研究证实了6的结构。提出了这种非典型加扰的机制，该机制很可能涉及酸催化的二吡咯甲烷合成的逆转。〜1H NMR进一步阐明了每种络合物的结构并显示了阻转异构现象的存在。电化学研究（循环伏安法，Osteryoung方波和线性扫描伏安法）表明，所得到的内消旋基团的基团电负性之和之间存在线性关系。卟啉和两种观察到的以环为中心的还原过程，内消旋取代基二茂铁基氧化过程和这四个关系可以在数学上进行量化。由于氧化的二茂铁基团具有强的吸电子特性，第二个以环为中心的氧化波落在二氯甲烷作为溶剂的势能窗之外。

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