Catalytic reduction of dinitrogen to silylamines by earth-abundant lanthanide and group 4 complexes

Anthony Wong, Francis Y. T. Lam, Matthew Hernandez, Jaden Lara, T. Michael Trinh, Rory P. Kelly, Tatsumi Ochiai, Guodong Rao, R. David Britt, Nikolas Kaltsoyannis, Polly L. Arnold

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Abstract

Dinitrogen is a challenging molecule to reduce to useful products under ambient conditions. The range of d-block metal complexes that can catalyze dinitrogen reduction to ammonia or tris(silyl)amines under ambient conditions has increased recently but lacks electropositive metal complexes, such as those of the f-block which lack filled d-orbitals that would support classical binding modes of N2. Here, metallacyclic phenolate structures with lanthanide or group 4 cations can bind dinitrogen and catalyze its conversion to bis(silyl)amines under ambient conditions. The formation of this unusual product is controlled by metallacycle sterics. The group 4 complexes featuring small cavities are most selective for bis(silyl)amine, while the lanthanide complexes and the solvated uranium(IV) congener, with larger cavities, can also make the conventional tris(silyl)amine product. These results offer new catalytic applications for plentiful titanium and the more earth-abundant members of the lanthanides that are also less toxic than many base metals used in catalysis.
Original languageEnglish
Article number100964
JournalChem Catalysis
Volume4
Early online date9 Apr 2024
DOIs
Publication statusE-pub ahead of print - 9 Apr 2024

Keywords

  • catalysis
  • dinitrogen reduction
  • N2RR
  • EPR
  • DFT
  • lanthanide
  • actinide
  • titaniu
  • zirconiu
  • aryloxid
  • silylamine

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