Anodic electrochemistry of mono- and dinuclear aminophenylferrocene and diphenylaminoferrocene complexes. Issue 17 (17th April 2018)

• Record Type: Journal Article
• Authors: Zhang, Ming-Xing; Zhang, Jing; Yin, Jun; Hartl, František; Liu, Sheng Hua
• Is Part Of: Dalton transactions. Volume 47:Issue 17(2018)
• Page Start: 6112
• Page End: 6123
• Publication Date: 2018-04-17
• Subjects: Chemistry, Inorganic -- Periodicals; Chemistry, Physical and theoretical -- Periodicals; Chemistry, Inorganic -- Periodicals; 546.05
• DOI: 10.1039/c8dt00584b
• Languages: English
• ISSNs: 1477-9226

Abstract

Abstract : The multistep anodic behavior of two series of nonlinear (di)aminophenylferrocene, and diphenylaminoferrocene complexes is reported. The first anodic steps all take place uniformly on the ferrocenyl units, followed by oxidation of the triphenylamine and Cp-diphenylamine moieties. Abstract : Two related three-membered series of nonlinear aminophenylferrocene and diphenylaminoferrocene complexes were prepared and characterized by 1 H and 13 C 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 complex1d 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 in1a–1f are localized preferentially on the ferrocenyl units, followed by oxidation of the TPA or TPPD moieties (absent in1d ). Irreversible oxidation of the ferrocene-appended strong donor DPA/MPA units in1d–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.