title: 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 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.
authors.affiliation: Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, California 91125, United States.
authors.forename: John S
authors.initials: JS
authors.lastname: Anderson
authors.affiliation: Department of Chemistry, Northwestern University, 2145 Sheridan Road, Evanston, Illinois 60208, United States.
authors.forename: George E
authors.initials: GE
authors.lastname: Cutsail
authors.affiliation: Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, California 91125, United States.
authors.forename: Jonathan
authors.initials: J
authors.lastname: Rittle
authors.affiliation: Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, California 91125, United States.
authors.forename: Bridget A
authors.initials: BA
authors.lastname: Connor
authors.affiliation: Department of Chemistry, Northwestern University, 2145 Sheridan Road, Evanston, Illinois 60208, United States.
authors.forename: William A
authors.initials: WA
authors.lastname: Gunderson
authors.affiliation: Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, California 91125, United States.
authors.forename: Limei
authors.initials: L
authors.lastname: Zhang
authors.affiliation: Department of Chemistry, Northwestern University, 2145 Sheridan Road, Evanston, Illinois 60208, United States.
authors.forename: Brian M
authors.initials: BM
authors.lastname: Hoffman
authors.affiliation: Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, California 91125, United States.
authors.forename: Jonas C
authors.initials: JC
authors.lastname: Peters
mesh_terms: D000641:Ammonia / Q000737:chemistry*; D001880:Boranes / Q000737:chemistry*; D002384:Catalysis; D043844:Crown Ethers / Q000737:chemistry*; D004578:Electron Spin Resonance Spectroscopy; D005290:Ferric Compounds / Q000737:chemistry*; D008958:Models, Molecular; D009584:Nitrogen / Q000737:chemistry*; D010084:Oxidation-Reduction
chemical_list: D001880:Boranes; D043844:Crown Ethers; D005290:Ferric Compounds; D000641:Ammonia; C557123:12-crown-4; D009584:Nitrogen