Characterization of an FeN-NH2 Intermediate Relevant to Catalytic N2 Reduction to NH3

The ability of certain transition metals to mediate the reduction of N-2 to NH3 has attracted broad interest in the biological and inorganic chemistry communities. Early transition metals such as Mo and W readily bind N-2 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-N-2 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(N-2)][Na(12-crown-4)] results in a new S = 1/2 Fe species. EPR, ENDOR, Mossbauer, and EXAFS analysis, coupled with a DFT study, unequivocally assign this new species as [(TPB)Fe equivalent to 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(N-2)][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 NN bond, as would be found in limiting distal or alternating mechanisms, respectively, is also provided.