Anodic electrochemistry of mono- and dinuclear aminophenylferrocene and diphenylaminoferrocene complexes
Anodic electrochemistry of mono- and dinuclear aminophenylferrocene and diphenylaminoferrocene complexes
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单核和双核氨基苯基二茂铁和二苯基氨基二茂铁配合物的阳极电化学
DOI：
10.1039/c8dt00584b
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发表时间：
2018
影响因子：
4
通讯作者：
Liu Sheng Hua
中科院分区：
文献类型：
--
作者：
Zhang Ming Xing;Zhang Jing;Yin Jun;Hartl Frantisek;Liu Sheng Hua
合成了两个相关的三元系列的非线性苯基氨基二茂铁和二苯基氨基二茂铁配合物，并用1H和13 C NMR进行了表征。第一个系列由4-（二苯基氨基）苯基二茂铁（TPA-Fc，1a）、其二甲氧基取代的四苯基苯二胺衍生物（M2 TPPD-Fc，1c）和三苯胺桥连的双（二茂铁基）络合物（Fc-TPA-Fc，1b）组成。第二个系列包括双（4-甲氧基苯基）氨基二茂铁（M2 DPA-Fc，1d）、4-甲氧基苯基氨基二茂铁（MPA-Fc）与N-苯基连接的末端TPA（1 e）和相应的双（MPA-Fc）与桥联TPA（1f）配合物。配合物1d的结构经单晶X射线衍射进一步证实。结合阳极伏安法、紫外-可见-近红外光谱电化学和密度泛函理论（DFT）计算，研究了多个氧化还原活性组分的整合对这些复合物的顺序氧化的影响. 1a-1f中的第一阳极步骤优先定位于二茂铁基单元上，随后是TPA或TPPD部分的氧化（1d中不存在）。在1d-1f中，二茂铁附加的强供体DPA/MPA单元的不可逆氧化终止了阳极系列。三苯胺桥联的双二茂铁（1b）和双（苯氨基二茂铁）（1f）配合物的单电子氧化引发它们容易的氧化还原反硝化为双阳离子双（二茂铁）产物。
Two related three-membered series of nonlinear aminophenylferrocene and diphenylaminoferrocene complexes were prepared and characterized by 1H and 13C NMR spectroscopy. The first series consists of 4-(diphenylamino)phenylferrocene (TPA-Fc, 1a), its dimethoxy-substituted tetraphenylphenylenediamine derivative (M2TPPD-Fc, 1c), and the triphenylamine-bridged bis(ferrocenyl) complex (Fc-TPA-Fc, 1b). The second series involves bis(4-methoxyphenyl)aminoferrocene (M2DPA-Fc, 1d), 4-methoxyphenylaminoferrocene (MPA-Fc) with N-phenyl-appended terminal TPA (1e), and the corresponding bis(MPA-Fc) complex with bridging TPA (1f). The structure of complex 1d was further confirmed by single crystal X-ray diffraction. Combined investigations, based on anodic voltammetry, UV-vis-NIR spectroelectrochemistry and density functional theory (DFT) calculations, were conducted to illustrate the influence of the integration of multiple redox-active components on the sequential oxidation of these complexes. The first anodic steps in 1a–1f are localized preferentially on the ferrocenyl units, followed by oxidation of the TPA or TPPD moieties (absent in 1d). Irreversible oxidation of the ferrocene-appended strong donor DPA/MPA units in 1d–1f terminates the anodic series. The one-electron oxidation of the triphenylamine-bridged diferrocenyl (1b) and bis(phenylaminoferrocenyl) (1f) complexes triggers their facile redox disproportionation to dicationic bis(ferrocenium) products.