Dinitrogen Reduction and Functionalization by a Siloxide Supported Thulium‐Potassium Complex for the Formation of Ammonia or Hydrazine Derivatives
2025

Dinitrogen Reduction and Functionalization by a Thulium-Potassium Complex

publication Evidence: high

Author Information

Author(s): Shivaraam R. A. Keerthi, Rajeshkumar Thayalan, Scopelliti Rosario, Z̆ivković Ivica Dr., Maron Laurent Prof., Mazzanti Marinella Prof.

Primary Institution: Ecole Polytechnique Fédérale de Lausanne (EPFL)

Hypothesis

Can a siloxide supported thulium-potassium complex facilitate the reduction and functionalization of dinitrogen?

Conclusion

The study successfully demonstrates the formation of ammonia and hydrazine derivatives from dinitrogen using a thulium-potassium complex.

Supporting Evidence

  • The thulium-potassium complex was able to reduce dinitrogen to form ammonia in 18% yield.
  • The study presents a rare example of a triply reduced N2 3− radical complex.
  • Functionalization of dinitrogen was achieved with electrophiles like H+ and MeOTf.

Takeaway

Scientists created a special compound that helps turn nitrogen gas into useful chemicals like ammonia, which is important for fertilizers.

Methodology

The synthesis and characterization of thulium-potassium complexes were performed using various techniques including SQUID, EPR, DFT, and X-Ray.

Limitations

The reactivity of the complexes in solution was limited, leading to significant decomposition over time.

Digital Object Identifier (DOI)

10.1002/anie.202414051

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