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

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(N(x)H(y)) species that can be characterized and, in turn, extrude NH3. By contrast, the direct protonation of Fe-N2 species to Fe(N(x)H(y)) 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 tri

SUBMITTER: Anderson JS 

PROVIDER: S-EPMC4603982 | biostudies-literature | 2015 Jun

REPOSITORIES: biostudies-literature