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Ebbe Nordlander. Portrait.

Ebbe Nordlander

Professor

Ebbe Nordlander. Portrait.

Sulfur-ligated iron(iv)-imido and iron(iv)-oxo complexes, which one is more reactive?

Author

  • Jagnyesh Kumar Satpathy
  • Rolly Yadav
  • Limashree Sahoo
  • Jens Uhlig
  • Ebbe Nordlander
  • Chivukula V. Sastri
  • Sam P. de Visser

Summary, in English

Mononuclear iron(iv)-oxo, iron(iv)-imido and iron(iv)-nitrido complexes are common catalytic cycle intermediates in enzymes, where the metal is typically linked to the protein through cysteinate or histidine sidechains. Enzymatic high-valent iron(iv)-imido and -nitrido intermediates have never been trapped and characterized; hence, there is uncertainty regarding their structure and function. Using biomimetic models, we have synthesized a novel N4S ligated iron(iv)-imido species as a faithful mimic of a corresponding intermediate in nitrogenase. The complex was characterized with a range of techniques, including UV-vis absorption spectroscopy, electrospray ionization mass spectrometry, resonance Raman spectroscopy and XANES and EXAFS methodologies. A comprehensive investigation combining reactivity studies and computational analysis compares the oxidative reactivity and chemical properties of the iron(iv)-imido complex with those of its oxo-analogue. Although the iron(iv)-oxo species is, in general, more reactive than its iron(iv)-tosylimido counterpart, the reverse trend is observed for the oxidation of specific para-substituted thioanisole substrates. Furthermore, an equatorial sulfur group in the ligand framework is seen to enhance the reactivity of thioanisole sulfoxidation. These studies show that high-valent metal-imido groups can be as powerful oxidants as iron(iv)-oxo entities in atom/group transfer reactions.

Department/s

  • Chemical Physics
  • LU Profile Area: Light and Materials
  • LTH Profile Area: Photon Science and Technology
  • LTH Profile Area: Nanoscience and Semiconductor Technology
  • NanoLund: Centre for Nanoscience

Publishing year

2025

Language

English

Publication/Series

Chemical Science

Document type

Journal article

Publisher

Royal Society of Chemistry

Topic

  • Physical Chemistry (including Surface- and Colloid Chemistry)

Status

Epub

ISBN/ISSN/Other

  • ISSN: 2041-6520