An Octahedral Coordination Complex of Iron(VI)

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Science  30 Jun 2006:
Vol. 312, Issue 5782, pp. 1937-1941
DOI: 10.1126/science.1128506

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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 FeEmbedded ImageN triple bond of 1.57 angstroms and a singlet Embedded Image ground electronic configuration. The compound is stable at 77 kelvin and yields a high-spin Fe(III) species upon warming.

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