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

Satpathy, Jagnyesh Kumar ; Yadav, Rolly ; Sahoo, Limashree ; Uhlig, Jens LU orcid ; Nordlander, Ebbe LU ; Sastri, Chivukula V. and de Visser, Sam P. (2025) In Chemical Science
Abstract

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... (More)

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.

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author
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organization
publishing date
type
Contribution to journal
publication status
epub
subject
in
Chemical Science
publisher
Royal Society of Chemistry
external identifiers
  • pmid:41311886
  • scopus:105023193947
ISSN
2041-6520
DOI
10.1039/d5sc07586f
language
English
LU publication?
yes
additional info
Publisher Copyright: This journal is © The Royal Society of Chemistry
id
0023504d-b381-4d7c-acef-12aeaa2d61b8
date added to LUP
2025-12-11 14:26:41
date last changed
2025-12-13 03:10:54
@article{0023504d-b381-4d7c-acef-12aeaa2d61b8,
  abstract     = {{<p>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 N<sub>4</sub>S 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.</p>}},
  author       = {{Satpathy, Jagnyesh Kumar and Yadav, Rolly and Sahoo, Limashree and Uhlig, Jens and Nordlander, Ebbe and Sastri, Chivukula V. and de Visser, Sam P.}},
  issn         = {{2041-6520}},
  language     = {{eng}},
  publisher    = {{Royal Society of Chemistry}},
  series       = {{Chemical Science}},
  title        = {{Sulfur-ligated iron(iv)-imido and iron(iv)-oxo complexes, which one is more reactive?}},
  url          = {{http://dx.doi.org/10.1039/d5sc07586f}},
  doi          = {{10.1039/d5sc07586f}},
  year         = {{2025}},
}