An Octahedral Coordination Complex of Iron(VI)

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 FeN triple bond of 1.57 angstroms and a singlet \batchmode \documentclass[fleqn,10pt,legalpaper]{article} \usepackage{amssymb} \usepackage{amsfonts} \usepackage{amsmath} \pagestyle{empty} \begin{document} \(\mathrm{d}_{xy}^{2}\) \end{document} ground electronic configuration. The compound is stable at 77 kelvin and yields a high-spin Fe(III) species upon warming.

[1]  David K. Johnson,et al.  Top Value-Added Chemicals from Biomass - Volume II—Results of Screening for Potential Candidates from Biorefinery Lignin , 2007 .

[2]  Christine M. Thomas,et al.  Characterization of the terminal iron(IV) imides [[PhBP(t)(Bu)2(pz')]Fe(IV)NAd]+. , 2006, Journal of the American Chemical Society.

[3]  S. Sligar,et al.  Cytochrome p450 compound I. , 2006, Journal of the American Chemical Society.

[4]  A. Ryabov,et al.  High-valent iron complexes with tetraamido macrocyclic ligands: structures, Mössbauer spectroscopy, and DFT calculations. , 2006, Journal of inorganic biochemistry.

[5]  C. Cummins.  Terminal, anionic carbide, nitride, and phosphide transition-metal complexes as synthetic entries to low-coordinate phosphorus derivatives. , 2006, Angewandte Chemie.

[6]  F. Neese,et al.  Effect of N-methylation of macrocyclic amine ligands on the spin state of iron(III): a tale of two fluoro complexes. , 2006, Inorganic chemistry.

[7]  W. Nam,et al.  A Thiolate-Ligated Nonheme Oxoiron(IV) Complex Relevant to Cytochrome P450 , 2005, Science.

[8]  K. Wieghardt,et al.  Octahedral non-heme non-oxo Fe(IV) species stabilized by a redox-innocent N-methylated cyclam-acetate ligand. , 2005, Journal of the American Chemical Society.

[9]  L. Que,et al.  High-valent nonheme iron. Two distinct iron(IV) species derived from a common iron(II) precursor. , 2005, Journal of the American Chemical Society.

[10]  D. Ming,et al.  Water alteration of rocks and soils on Mars at the Spirit rover site in Gusev crater , 2005, Nature.

[11]  S. Shima,et al.  Mössbauer studies of the iron-sulfur cluster-free hydrogenase: the electronic state of the mononuclear Fe active site. , 2005, Journal of the American Chemical Society.

[12]  C. Cramer,et al.  Structures of nonheme oxoiron(IV) complexes from X-ray crystallography, NMR spectroscopy, and DFT calculations. , 2005, Angewandte Chemie.

[13]  Sason Shaik,et al.  Theoretical investigation of C--H hydroxylation by (N4Py)Fe(IV)=O(2+): an oxidant more powerful than P450? , 2005, Journal of the American Chemical Society.

[14]  Frank Neese,et al.  The geometric and electronic structure of [(cyclam-acetato)Fe(N)]+: a genuine iron(v) species with a ground-state spin S = 1/2. , 2005, Angewandte Chemie.

[15]  Ilme Schlichting,et al.  Structure and chemistry of cytochrome P450. , 2005, Chemical reviews.

[16]  U. Bonnes,et al.  Jarosite and Hematite at Meridiani Planum from Opportunity's Mössbauer Spectrometer , 2004, Science.

[17]  Mi Hee Lim,et al.  Structural insights into nonheme alkylperoxoiron(III) and oxoiron(IV) intermediates by X-ray absorption spectroscopy. , 2004, Journal of the American Chemical Society.

[18]  J. Peters,et al.  A tetrahedrally coordinated L3Fe-Nx platform that accommodates terminal nitride (Fe(IV)N) and dinitrogen (Fe(I)-N2-Fe(I)) ligands. , 2004, Journal of the American Chemical Society.

[19]  L. Que,et al.  Nonheme FeIVO complexes that can oxidize the C-H bonds of cyclohexane at room temperature. , 2004, Journal of the American Chemical Society.

[20]  F. Neese,et al.  Mixed-Valent {FeIV(μ-O)(μ-carboxylato)2FeIII}3+ Core , 2003 .

[21]  Carsten Krebs,et al.  The first direct characterization of a high-valent iron intermediate in the reaction of an alpha-ketoglutarate-dependent dioxygenase: a high-spin FeIV complex in taurine/alpha-ketoglutarate dioxygenase (TauD) from Escherichia coli. , 2003, Biochemistry.

[22]  Mi Hee Lim,et al.  Crystallographic and spectroscopic characterization of a nonheme Fe(IV)-O complex. , 2003, Science.

[23]  Jia-Qian Jiang,et al.  Progress in the development and use of ferrate(VI) salt as an oxidant and coagulant for water and wastewater treatment. , 2002, Water research.

[24]  K. Nakamoto.  Resonance Raman spectra and biological significance of high-valent iron(IV,V) porphyrins , 2002 .

[25]  L. Que,et al.  A synthetic model for the putative Fe(IV)(2)O(2) diamond core of methane monooxygenase intermediate Q. , 2001, Journal of the American Chemical Society.

[26]  Maarten Merkx,et al.  Dioxygen Activation and Methane Hydroxylation by Soluble Methane Monooxygenase: A Tale of Two Irons and Three Proteins. , 2001, Angewandte Chemie.

[27]  F. Neese,et al.  Molecular and Electronic Structure of [MnVN(cyclam−acetato)]PF6. A Combined Experimental and DFT Study , 2001 .

[28]  S. Sligar,et al.  Hydroxylation of camphor by reduced oxy-cytochrome P450cam: mechanistic implications of EPR and ENDOR studies of catalytic intermediates in native and mutant enzymes. , 2001, Journal of the American Chemical Society.

[29]  K Wieghardt,et al.  Mononuclear (nitrido)iron(V) and (oxo)iron(IV) complexes via photolysis of [(cyclam-acetato)FeIII(N3)]+ and ozonolysis of [(cyclam-acetato)FeIII(O3SCF3)]+ in water/acetone mixtures. , 2000, Inorganic chemistry.

[30]  J Berendzen,et al.  The catalytic pathway of cytochrome p450cam at atomic resolution. , 2000, Science.

[31]  Licht,et al.  Energetic Iron(VI) chemistry: the super-iron battery , 1999, Science.

[32]  Eckhard Bill,et al.  Photolysis of cis- and trans-[FeIII(cyclam)(N3)2]+ Complexes: Spectroscopic Characterization of a Nitridoiron(V) Species , 1999 .

[33]  B J Lemon,et al.  X-ray crystal structure of the Fe-only hydrogenase (CpI) from Clostridium pasteurianum to 1.8 angstrom resolution. , 1998, Science.

[34]  H. Beinert,et al.  Iron-sulfur clusters: nature's modular, multipurpose structures. , 1997, Science.

[35]  P. Laszlo,et al.  A Novel Oxidizing Reagent Based on Potassium Ferrate(VI)(1). , 1996, The Journal of organic chemistry.

[36]  Michel Frey,et al.  Crystal structure of the nickel–iron hydrogenase from Desulfovibrio gigas , 1995, Nature.

[37]  F. Kazama.  Inactivation of coliphage Qβ by potassium ferrate , 1994 .

[38]  N. N. GREENWOOD,et al.  Mossbauer Spectroscopy , 1966, Nature.

[39]  R. Schrock,et al.  Synthesis of an iron(IV) cyanide complex that contains the triamido amine ligand [(tert-BuMe2SiNCH2CH2)3N]3- , 1994 .