Anodic electrochemistry of mono- and dinuclear aminophenylferrocene and diphenylaminoferrocene complexes

Zhang, M.-X., Zhang, J., Yin, J., Hartl, F. ORCID: https://orcid.org/0000-0002-7013-5360 and Liu, S. H. (2018) Anodic electrochemistry of mono- and dinuclear aminophenylferrocene and diphenylaminoferrocene complexes. Dalton Transactions, 47 (17). pp. 6112-6123. ISSN 1364-5447 doi: 10.1039/c8dt00584b

Abstract/Summary

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

Item Type	Article
URI	https://reading-clone.eprints-hosting.org/id/eprint/79077
Identification Number/DOI	10.1039/c8dt00584b
Refereed	Yes
Divisions	Life Sciences > School of Chemistry, Food and Pharmacy > Department of Chemistry
Publisher	Royal Society of Chemistry
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