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Related Experiment Videos

Polar effects in nitride coupling reactions.

Sean B Seymore1, Seth N Brown

  • 1Department of Chemistry and Biochemistry, 251 Nieuwland Science Hall, University of Notre Dame, Notre Dame, Indiana 46556-5670, USA.

Inorganic Chemistry
|February 5, 2002
PubMed
Summary

This study shows that molybdenum nitride reacts with osmium nitride to form molecular nitrogen, primarily through mixed-metal coupling. A bridging nitride complex was also formed, highlighting kinetic effects in nitride coupling reactions.

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Inorganic chemistry·2022

Area of Science:

  • Inorganic Chemistry
  • Organometallic Chemistry
  • Coordination Chemistry

Background:

  • Nitride complexes are crucial intermediates in nitrogen fixation and catalysis.
  • Understanding heterometallic nitride reactivity is key to developing new catalytic systems.
  • Molybdenum and osmium nitride complexes offer distinct electronic properties for reactivity studies.

Purpose of the Study:

  • To investigate the reaction between a nucleophilic molybdenum nitride and an electrophilic osmium nitride.
  • To elucidate the mechanism of dinitrogen formation and identify reaction products.
  • To explore the kinetics and origins of heterometallic nitride coupling.

Main Methods:

  • Reaction of (Et(2)NCS(2))(3)MoN with TpOsNCl(2).
  • Isotopic labeling experiments to trace nitrogen origins.

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  • Crystallographic characterization of the mu-nitrido complex product.

    • Main Results:

    • Formation of molecular nitrogen (N(2)) via mixed-metal (molybdenum-osmium) coupling (>96%).
    • Synthesis of a heterobimetallic mu-nitrido complex, TpOsCl(2)(mu-N)Mo(S(2)CNEt(2))(3), with the bridge primarily from osmium (82%).
    • Observation that heterometallic coupling is kinetically favored over homometallic coupling.

    Conclusions:

    • Demonstrated efficient dinitrogen formation from heterometallic nitride coupling.
    • The asymmetric bridging nitride structure suggests preferential bonding interactions.
    • Kinetic preference for heterometallic coupling provides insights into nitride transfer mechanisms.