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A Mononuclear Nonheme Iron(V)-Imido Complex.

Seungwoo Hong1,2, Kyle D Sutherlin3, Anil Kumar Vardhaman1

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Journal of the American Chemical Society
|June 20, 2017
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Summary

Researchers synthesized the first mononuclear nonheme iron(V)-imido complex using a tetraamido macrocyclic ligand (TAML). This novel iron complex exhibits unique spectroscopic properties and reactivity in C-H functionalization and nitrene transfer reactions.

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Area of Science:

  • Inorganic Chemistry
  • Organometallic Chemistry
  • Bioinorganic Chemistry

Background:

  • Mononuclear nonheme iron(V)-oxo complexes are known.
  • The synthesis and characterization of novel high-valent iron complexes are crucial for understanding their reactivity.

Purpose of the Study:

  • To report the first example of a mononuclear nonheme iron(V)-imido complex.
  • To characterize the complex spectroscopically.
  • To investigate its reactivity in C-H functionalization and nitrene transfer reactions.

Main Methods:

  • Synthesis of the iron(V)-imido complex bearing a tetraamido macrocyclic ligand (TAML).
  • Spectroscopic characterization including determination of oxidation state, Fe-N bond length, and Fe-N vibration.
  • Reactivity studies focusing on C-H bond functionalization and nitrene transfer.

Main Results:

  • The first mononuclear nonheme iron(V)-imido complex, [(TAML)Fe(NTs)]- (1), was successfully synthesized.
  • Spectroscopic data confirmed an S = 1/2 Fe(V) oxidation state, an Fe-N bond length of 1.65(4) Å, and an Fe-N vibration at 817 cm⁻¹.
  • Complex 1 demonstrated reactivity in C-H bond functionalization and nitrene transfer reactions.

Conclusions:

  • This study presents a novel iron(V)-imido complex with unique structural and spectroscopic features.
  • The findings expand the scope of known mononuclear nonheme iron complexes.
  • The demonstrated reactivity highlights the potential of this complex in catalytic applications.