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  3. A Structurally Authenticated Closed-shell Iron(iv) Oxo Ferryl Complex: Synthesis, Properties, And Reactivity.
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  3. A Structurally Authenticated Closed-shell Iron(iv) Oxo Ferryl Complex: Synthesis, Properties, And Reactivity.

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A Structurally Authenticated Closed-Shell Iron(IV) Oxo Ferryl Complex: Synthesis, Properties, and Reactivity.

Weiqing Mao1, Zihan Zhang1, Martin Keilwerth1

  • 1Department of Chemistry and Pharmacy, Inorganic Chemistry, Friedrich-Alexander-Universität Erlangen-Nürnberg (FAU), Egerlandstraße 1, 91058 Erlangen, Germany.

Journal of the American Chemical Society
|March 19, 2026

View abstract on PubMed

Summary
This summary is machine-generated.

Researchers synthesized a stable iron(IV) oxo complex using a tripodal tris-N-heterocyclic carbene ligand. This nonmagnetic complex exhibits a short iron-oxygen bond and mediates oxygen-atom transfer reactions.

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Area of Science:

  • Inorganic Chemistry
  • Organometallic Chemistry
  • Coordination Chemistry

Background:

  • Iron-oxo complexes are crucial in biological and catalytic oxidation reactions.
  • Stabilizing high-valent iron species is challenging due to their reactivity.
  • N-heterocyclic carbene (NHC) ligands offer robust coordination for stabilizing reactive metal centers.

Purpose of the Study:

  • To synthesize and characterize a closed-shell, nonmagnetic iron(IV) oxo complex.
  • To investigate the structural, spectroscopic, and electronic properties of the iron(IV) oxo species.
  • To explore the reactivity of the synthesized complex in oxygen-atom transfer reactions.

Main Methods:

  • Synthesis of iron complexes using tris-N-heterocyclic carbene (NHC) ligands.
  • Oxidation reactions using N₂O, [Cp₂Fe][PF₆], and trimethylamine N-oxide (TMAO).
  • Photolysis of ferrous sulfoxide isotopomers.
  • Comprehensive characterization including X-ray crystallography, NMR, IR, UV-vis, Mössbauer spectroscopy, and elemental analysis.
  • Computational analyses (DFT) and cyclic voltammetry.

    • Main Results:

    • Successful synthesis and isolation of a diamagnetic iron(IV) oxo complex, [(Me₂TIMMNMeS)FeIV(O)](PF₆)₂, stabilized by a tripodal NHC ligand.
    • Characterization revealed a short Fe-O bond (1.576 Å) and Mössbauer isomer shift indicative of the Fe(IV) state.
    • Computational studies supported an Fe≡O triple bond.
    • The complex demonstrated intermolecular oxygen-atom transfer capabilities.
    • Cyclic voltammetry suggested a reversible redox event corresponding to an Fe(V) oxo species.

    Conclusions:

    • A stable, nonmagnetic iron(IV) oxo complex has been synthesized and fully characterized.
    • The complex features a short Fe-O bond and likely possesses an Fe≡O triple bond.
    • This iron(IV) oxo complex shows potential as an oxidant in catalytic oxygen-atom transfer reactions.
    • The study provides insights into the stabilization and reactivity of high-valent iron-oxo species.