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A tungstenVI nitride having a W2(mu-N)2 core.

Zachary J Tonzetich1, Richard R Schrock, Keith M Wampler

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Inorganic Chemistry
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Researchers synthesized a tungsten nitrido species and characterized its dimeric structure using X-ray and spectroscopic methods. This tungsten nitride can be converted to a monomeric imido species and reduced to a radical anion.

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Area of Science:

  • Organometallic Chemistry
  • Inorganic Chemistry
  • Tungsten Chemistry

Background:

  • Tungsten nitrido complexes are important in catalysis and materials science.
  • Understanding the reactivity and electronic structure of tungsten nitrides is crucial for developing new applications.

Purpose of the Study:

  • To synthesize and characterize a novel tungsten nitrido species.
  • To investigate the reactivity of the tungsten nitride with electrophiles and reducing agents.
  • To elucidate the electronic structure and bonding in the tungsten nitrido core.

Main Methods:

  • Synthesis of tungsten nitrido species from alkylidyne precursors and organonitriles.
  • X-ray crystallography for solid-state structural determination.
  • 15N NMR spectroscopy and vibrational spectroscopy for solution characterization.
  • Electrochemical reduction and reaction with metallocenes for generating radical anions.
  • Density functional theory (DFT) calculations for electronic structure analysis.

Main Results:

  • The dimeric tungsten nitrido species [W(mu-N)(CH2-t-Bu)(OAr)2]2 was successfully synthesized and characterized.
  • Reaction with trimethylsilyl trifluoromethanesulfonate yielded a monomeric trimethylsilyl imido species.
  • Electrochemical and chemical reduction afforded the corresponding radical anion.
  • DFT calculations revealed insights into the electronic transitions within the tungsten nitrido core.

Conclusions:

  • The study reports the synthesis and comprehensive characterization of a novel tungsten nitrido species.
  • The reactivity studies demonstrate the versatility of the tungsten nitrido core in forming imido species and radical anions.
  • Electronic structure calculations provide a theoretical basis for understanding the observed properties and transitions.