Comparison of the reactivity of nonheme iron(IV)-oxo versus iron(IV)-imido complexes: which is the better oxidant?

Which is better? The first detailed comparison of the reactivity of nonheme iron(IV)-imido versus nonheme iron(IV)-oxo intermediates with substrates is presented. The iron(IV)-imido variant reacts with sulfides five times faster than iron(IV)-oxo, whereas the reverse trend is observed for hydrogen atom abstraction. These observed trends are analyzed and explained.

[1]  Erich Leitner,et al.  Inversion of enantioselectivity of a mononuclear non-heme iron(II)-dependent hydroxylase by tuning the interplay of metal-center geometry and protein structure. , 2013, Angewandte Chemie.

[2]  Matthew G. Quesne,et al.  Secondary Coordination Sphere Influence on the Reactivity of Nonheme Iron(II) Complexes: An Experimental and DFT Approach , 2013, Journal of the American Chemical Society.

[3]  T. Betley,et al.  Complex N-Heterocycle Synthesis via Iron-Catalyzed, Direct C–H Bond Amination , 2013, Science.

[4]  C. Che,et al.  Nonheme iron-mediated amination of C(sp3)-H bonds. Quinquepyridine-supported iron-imide/nitrene intermediates by experimental studies and DFT calculations. , 2013, Journal of the American Chemical Society.

[5]  S. D. de Visser,et al.  Generation of a high-valent iron imido corrolazine complex and NR group transfer reactivity. , 2013, Inorganic chemistry.

[6]  S. D. de Visser,et al.  Does hydrogen-bonding donation to manganese(IV)-oxo and iron(IV)-oxo oxidants affect the oxygen-atom transfer ability? A computational study. , 2013, Chemistry.

[7]  Xuri Huang,et al.  Comparative insight into electronic properties and reactivities toward C-H bond activation by iron(IV)-nitrido, iron(IV)-oxo, and iron(IV)-sulfido complexes: a theoretical investigation. , 2013, Inorganic chemistry.

[8]  L. Que,et al.  High-valent nonheme iron-oxo complexes: Synthesis, structure, and spectroscopy , 2013 .

[9]  Y. J. Kang,et al.  Correction: Corrigendum: MicroRNA122 is a key regulator of α-fetoprotein expression and influences the aggressiveness of hepatocellular carcinoma , 2012 .

[10]  P. Hildebrandt,et al.  Lewis acid trapping of an elusive copper-tosylnitrene intermediate using scandium triflate. , 2012, Journal of the American Chemical Society.

[11]  C. Che,et al.  Practical iron-catalyzed atom/group transfer and insertion reactions , 2012 .

[12]  K. Ray,et al.  The biology and chemistry of high-valent iron–oxo and iron–nitrido complexes , 2012, Nature Communications.

[13]  S. D. de Visser,et al.  Nonheme ferric hydroperoxo intermediates are efficient oxidants of bromide oxidation. , 2011, Chemical communications.

[14]  G. N. Sastry,et al.  Effect of the axial ligand on substrate sulfoxidation mediated by iron(IV)-oxo porphyrin cation radical oxidants. , 2011, Chemistry.

[15]  Patrick L. Holland,et al.  Selectivity and mechanism of hydrogen atom transfer by an isolable imidoiron(III) complex. , 2011, Journal of the American Chemical Society.

[16]  Christopher J. Chang,et al.  A seven-coordinate iron platform and its oxo and nitrene reactivity , 2011 .

[17]  S. Fukuzumi,et al.  Metal ion effect on the switch of mechanism from direct oxygen transfer to metal ion-coupled electron transfer in the sulfoxidation of thioanisoles by a non-heme iron(IV)-oxo complex. , 2011, Journal of the American Chemical Society.

[18]  T. Betley,et al.  Catalytic C-H bond amination from high-spin iron imido complexes. , 2011, Journal of the American Chemical Society.

[19]  W. Thiel,et al.  Theoretical study on the mechanism of the oxygen activation process in cysteine dioxygenase enzymes. , 2011, Journal of the American Chemical Society.

[20]  C. Che,et al.  Catalysis by Fe=X Complexes (X = NR, CR2) , 2011 .

[21]  J. Mayer,et al.  Thermochemistry of proton-coupled electron transfer reagents and its implications. , 2010, Chemical reviews.

[22]  F. Neese,et al.  Analysis of reaction channels for alkane hydroxylation by nonheme iron(IV)-oxo complexes. , 2010, Angewandte Chemie.

[23]  S. D. de Visser,et al.  Unprecedented rate enhancements of hydrogen-atom transfer to a manganese(V)-oxo corrolazine complex. , 2010, Angewandte Chemie.

[24]  Sam P. de Visser,et al.  Trends in substrate hydroxylation reactions by heme and nonheme iron(IV)-oxo oxidants give correlations between intrinsic properties of the oxidant with barrier height , 2010 .

[25]  Jeremy M. Smith,et al.  Formation of ammonia from an iron nitrido complex. , 2009, Angewandte Chemie.

[26]  J. Phillips,et al.  Mechanism of the iron-mediated alkene aziridination reaction: experimental and computational investigations. , 2009, Inorganic chemistry.

[27]  K. Hodgson,et al.  Reactive intermediates in oxygenation reactions with mononuclear nonheme iron catalysts. , 2009, Angewandte Chemie.

[28]  G. van Koten,et al.  Mononuclear non-heme iron enzymes with the 2-His-1-carboxylate facial triad: recent developments in enzymology and modeling studies. , 2008, Chemical Society reviews.

[29]  P. Comba,et al.  The mechanism of the (bispidine)copper(II)-catalyzed aziridination of styrene: a combined experimental and theoretical study. , 2008, Chemistry.

[30]  Haobin Wang,et al.  Thermodynamics of hydrogen atom transfer to a high-valent iron imido complex. , 2008, Journal of the American Chemical Society.

[31]  J. Chang,et al.  Highly efficient ruthenium(II) porphyrin catalyzed amidation of aldehydes. , 2008, Angewandte Chemie.

[32]  Joyce Wei Wei Chang and,et al.  Highly Efficient Ruthenium(II) Porphyrin Catalyzed Amidation of Aldehydes , 2007 .

[33]  S. Shaik,et al.  Axial ligand tuning of a nonheme iron(IV)–oxo unit for hydrogen atom abstraction , 2007, Proceedings of the National Academy of Sciences.

[34]  S. D. de Visser,et al.  The mechanism of cysteine oxygenation by cysteine dioxygenase enzymes. , 2007, Journal of the American Chemical Society.

[35]  F. Neese,et al.  Characterization of a genuine iron(V)-nitrido species by nuclear resonant vibrational spectroscopy coupled to density functional calculations. , 2007, Journal of the American Chemical Society.

[36]  R. Eldik Fascinating inorganic/bioinorganic reaction mechanisms☆ , 2007 .

[37]  S. D. de Visser,et al.  Combined experimental and theoretical study on aromatic hydroxylation by mononuclear nonheme iron(IV)-oxo complexes. , 2007, Inorganic chemistry.

[38]  Michael J. Zdilla,et al.  Mechanism of catalytic aziridination with manganese corrole: the often postulated high-valent Mn(V) imido is not the group transfer reagent. , 2006, Journal of the American Chemical Society.

[39]  Sam P. de Visser,et al.  What Factors Influence the Ratio of C¿H Hydroxylation versus C¿C Epoxidation by a Nonheme Cytochrome P450 Biomimetic? , 2006 .

[40]  L. Que,et al.  A tosylimido analogue of a nonheme oxoiron(IV) complex. , 2006, Angewandte Chemie.

[41]  Sam P. de Visser,et al.  Propene activation by the oxo-iron active species of taurine/α- ketoglutarate dioxygenase (TauD) enzyme. How does the catalysis compare to heme-enzymes? , 2006 .

[42]  Frank Neese,et al.  An Octahedral Coordination Complex of Iron(VI) , 2006, Science.

[43]  Sason Shaik,et al.  Two-state reactivity in alkane hydroxylation by non-heme iron-oxo complexes. , 2006, Journal of the American Chemical Society.

[44]  D. P. Goldberg,et al.  Hydrogen atom abstraction by a high-valent manganese(V)-oxo corrolazine. , 2006, Inorganic chemistry.

[45]  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.

[46]  M. Mehn,et al.  Mid- to high-valent imido and nitrido complexes of iron. , 2006, Journal of inorganic biochemistry.

[47]  D. Nelson Cytochrome P450: Structure, Mechanism, and Biochemistry, 3rd ed Edited by Paul R. Ortiz de Montellano (University of California, San Francisco). Kluwer Academic/Plenum Publishers: New York. 2005. xx + 690 pp. $149.00. ISBN 0-306-48324-6. , 2005 .

[48]  S. V. Kryatov,et al.  Kinetics and mechanisms of formation and reactivity of non-heme iron oxygen intermediates. , 2005, Chemical reviews.

[49]  S. Shaik,et al.  Sulfoxidation mechanisms catalyzed by cytochrome P450 and horseradish peroxidase models: spin selection induced by the ligand. , 2005, Biochemistry.

[50]  M. Abu‐Omar,et al.  Reaction mechanisms of mononuclear non-heme iron oxygenases. , 2005, Chemical reviews.

[51]  L. Que,et al.  Dioxygen activation at mononuclear nonheme iron active sites: enzymes, models, and intermediates. , 2004, Chemical reviews.

[52]  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.

[53]  L. Que,et al.  Intramolecular aromatic amination through iron-mediated nitrene transfer. , 2003, Angewandte Chemie.

[54]  J. Mayer,et al.  Oxidation of C-H bonds by [(bpy)2(py)RuIVO]2+ occurs by hydrogen atom abstraction. , 2003, Journal of the American Chemical Society.

[55]  J. Groves The bioinorganic chemistry of iron in oxygenases and supramolecular assemblies , 2003, Proceedings of the National Academy of Sciences of the United States of America.

[56]  S. Fukuzumi,et al.  Mechanisms of Sulfoxidation Catalyzed by High-Valent Intermediates of Heme Enzymes: Electron-Transfer vs Oxygen-Transfer Mechanism , 1999 .

[57]  James M. Mayer,et al.  HYDROGEN ATOM ABSTRACTION BY METAL-OXO COMPLEXES : UNDERSTANDING THE ANALOGY WITH ORGANIC RADICAL REACTIONS , 1998 .

[58]  J. Dawson,et al.  Heme-Containing Oxygenases. , 1996, Chemical reviews.

[59]  Jin‐Pei Cheng,et al.  Substituent effects on the stabilities of phenoxyl radicals and the acidities of phenoxyl radical cations , 1991 .

[60]  D. Mansuy,et al.  Formation of an iron(III)-porphyrin complex with a nitrene moiety inserted into an iron-nitrogen bond during alkene aziridination by (tosylimidoiodo)benzene catalyzed by iron(III) porphyrins , 1986 .

[61]  S. Gellman,et al.  Functionalized nitrogen atom transfer catalyzed by cytochrome P-450 , 1985 .

[62]  R. White,et al.  Aliphatic hydroxylation by cytochrome P-450: evidence for rapid hydrolysis of an intermediate iron-nitrene complex , 1984 .

[63]  P. Gans,et al.  Iron porphyrin-nitrene complexes: preparation from 1,1-dialkylhydrazines. Electronic structure from NMR, Moessbauer, and magnetic susceptibility studies and crystal structure of the [tetrakis(p-chlorophenyl)porphyrinato][(2,2,6,6-tetramethyl-1-piperidyl)nitrene]iron complex , 1984 .

[64]  L. E. Friedrich The two hydrogen-oxygen bond-dissociation energies of hydroquinone , 1983 .

[65]  D. Mansuy,et al.  Isolation of an iron-nitrene complex from the dioxygen- and iron porphyrin-dependent oxidation of a hydrazine , 1982 .