Synthesis of a low-spin iron(III) complex from its high-spin iron(II) counterpart: What causes redox potentials that disobey the expected trends?

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Abstract

We discuss here the chemical oxidation of a high-spin iron(II) complex containing the 1,3-bis(2′-benzimidazolylimino)isoindoline ligand (HL 1) using tris(4-bromophenyl)aminium hexachloroantimonate (Magic Blue). The product was X-ray structurally, spectroscopically (Mössbauer, FT-IR, UV-vis) and electrochemically characterized and can be formulated as [FeIII(L1)2][FeIII(L 1H- 2)(L1)] (1), a low-spin iron(III) 1D coordination polymer with strong H-bonds between ligands and N,N-dimethylformamide (DMF) solvent molecules in the solid phase. The redox potential of the [FeII(L1)2] complex at - 407 mV vs. ferrocene in DMF is shifted to the anodic direction only by 12 mV in the case of 1 against the expected cathodic shift upon proton loss from the ligand. The difference in the spin state of [FeII(L1)2] and 1, and the impact of H-bonds (detected in the crystal structure) that are able to facilitate proton-coupled electron transfer have been considered as plausible explanations.

Original languageEnglish
Pages (from-to)152-155
Number of pages4
JournalInorganic Chemistry Communications
Volume27
DOIs
Publication statusPublished - Jan 1 2013

Keywords

  • Iron
  • Isoindoline
  • Mössbauer
  • Oxidation
  • Proton-coupled electron transfer
  • Redox chemistry

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry
  • Materials Chemistry

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