Octahedral Coordination Complex of Iron(VI)

• Published in: Science (American Association for the Advancement of Science) Vol. 312; no. 5782; pp. 1937 - 1941
• Main Authors: Berry, John F, Bill, Eckhard, Bothe, Eberhard, George, Serena DeBeer, Mienert, Bernd, Neese, Frank, Wieghardt, Karl
• Format: Journal Article
• Language: English
• Published: Washington, DC American Association for the Advancement of Science 30-06-2006; The American Association for the Advancement of Science
• Subjects: Chemical bonds; Chemical compounds; Chemical Phenomena; Chemistry; Chemistry, Physical; Cold Temperature; Coordination compounds; Covalent bonds; Electrochemistry; Electrons; Exact sciences and technology; Ferrates; Inorganic chemistry and origins of life; Ions; Iron; Iron - chemistry; Isomerism; Isomers; Ligands; Models, Molecular; Molecular Structure; Nitrogen - chemistry; Orbitals; Organometallic Compounds - chemistry; Oxidation; Oxidation-Reduction; Oxygen; Photochemistry; Photolysis; Preparations and properties; Species; Spectrophotometry, Infrared; Spectroscopy, Mossbauer; Spectrum Analysis; Absorption spectrometry; Hexavalent metal Complexes; Iron VI Complexes; X ray absorption spectrometry; Ligand; Nitrido complex; Density functional method; Geometrical configuration; Transition metal Complexes; Photochemical reaction; Chemical synthesis
• ISSN: 0036-8075; 1095-9203
• DOI: 10.1126/science.1128506

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 FeFormula N triple bond of 1.57 angstroms and a singlet [Formula: see text] ground electronic configuration. The compound is stable at 77 kelvin and yields a high-spin Fe(III) species upon warming.