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Abstract:
The hexavalent state, considered to be the highest oxidation level accessible for iron, has previously been found only in the tetrahedral ferrate dianion, FeO42–. We report the photochemical synthesis of another Fe(VI) compound, an octahedrally coordinated dication bearing a terminal nitrido ligand. Mössbauer and x-ray absorption spectra, supported by density functional theory, are consistent with the octahedral structure having an Fe≡N triple bond of 1.57 angstroms and a singlet d2xy ground electronic configuration. The compound is stable at 77 kelvin and yields a high-spin Fe(III) species upon warming.
