Characterization of an Fe≡N-NH2 Intermediate Relevant to Catalytic N2 Reduction to NH3

John S. Anderson, George E. Cutsail, Jonathan Rittle, Bridget A. Connor, William A. Gunderson, Limei Zhang*, Brian M. Hoffman, Jonas C. Peters

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

89 Scopus citations

Abstract

The ability of certain transition metals to mediate the reduction of N2 to NH3 has attracted broad interest in the biological and inorganic chemistry communities. Early transition metals such as Mo and W readily bind N2 and mediate its protonation at one or more N atoms to furnish M(NxHy) species that can be characterized and, in turn, extrude NH3. By contrast, the direct protonation of Fe-N2 species to Fe(NxHy) products that can be characterized has been elusive. Herein, we show that addition of acid at low temperature to [(TPB)Fe(N2)][Na(12-crown-4)] results in a new S = 1/2 Fe species. EPR, ENDOR, Mössbauer, and EXAFS analysis, coupled with a DFT study, unequivocally assign this new species as [(TPB)Fe≡N-NH2]+, a doubly protonated hydrazido(2-) complex featuring an Fe-to-N triple bond. This unstable species offers strong evidence that the first steps in Fe-mediated nitrogen reduction by [(TPB)Fe(N2)][Na(12-crown-4)] can proceed along a distal or "Chatt-type" pathway. A brief discussion of whether subsequent catalytic steps may involve early or late stage cleavage of the N-N bond, as would be found in limiting distal or alternating mechanisms, respectively, is also provided. (Chemical Equation Presented).

Original languageEnglish (US)
Pages (from-to)7803-7809
Number of pages7
JournalJournal of the American Chemical Society
Volume137
Issue number24
DOIs
StatePublished - Jun 24 2015

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Fingerprint Dive into the research topics of 'Characterization of an Fe≡N-NH<sub>2</sub> Intermediate Relevant to Catalytic N<sub>2</sub> Reduction to NH<sub>3</sub>'. Together they form a unique fingerprint.

Cite this