A Mononuclear Nonheme Iron(IV)–Amido Complex Relevant for the Compound II Chemistry of Cytochrome P450

Lu, Xiaoyan; Li, Xiao-Xi; Seo, Mi Sook; Lee, Yong-Min; Clémancey, Martin; Maldivi, Pascale; Latour, Jean-Marc; Sarangi, Ritimukta; Fukuzumi, Shunichi; Nam, Wonwoo

doi:10.1021/jacs.8b11045

Title: A Mononuclear Nonheme Iron(IV)–Amido Complex Relevant for the Compound II Chemistry of Cytochrome P450

Abstract

A mononuclear nonheme iron(IV)–amido complex bearing a tetraamido macrocyclic ligand, [(TAML)Fe^IV(NHTs)]^- (1), was synthesized via a hydrogen atom (H atom) abstraction reaction of an iron(V)–imido complex, [(TAML)FeV(NTs)]- (2), and fully characterized using various spectroscopies. We then investigated (1) the pK_a of 1, (2) the reaction of 1 with a carbon-centered radical, and (3) the H atom abstraction reaction of 1. To the best of our knowledge, the present study reports for the first time the synthesis and chemical properties/reactions of a high-valent iron(IV)–amido complex.

Authors:

Lu, Xiaoyan ^[1]; Li, Xiao-Xi ^[1]; Seo, Mi Sook ^[1];

^[1]; Clémancey, Martin ^[2]; Maldivi, Pascale ^[2]; Latour, Jean-Marc ^[2];

^[3];

^[1];

^[1]

Ewha Womans Univ., Seoul (Korea). Dept. of Chemistry and Nano Science
Univ. Grenoble Alpes, Genoble (France)
SLAC National Accelerator Lab., Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource (SSRL)

Publication Date:: Sat Nov 24 00:00:00 EST 2018

Research Org.:: SLAC National Accelerator Lab., Menlo Park, CA (United States)

Sponsoring Org.:: USDOE Office of Science (SC), Biological and Environmental Research (BER); National Institutes of Health (NIH)

OSTI Identifier:: 1493335

Grant/Contract Number:: AC02-76SF00515; P41GM103393; A0040807648

Resource Type:: Accepted Manuscript

Journal Name:: Journal of the American Chemical Society

Additional Journal Information:: Journal Volume: 141; Journal Issue: 1; Journal ID: ISSN 0002-7863

Publisher:: American Chemical Society (ACS)

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats


                    Lu, Xiaoyan, Li, Xiao-Xi, Seo, Mi Sook, Lee, Yong-Min, Clémancey, Martin, Maldivi, Pascale, Latour, Jean-Marc, Sarangi, Ritimukta, Fukuzumi, Shunichi, and Nam, Wonwoo. A Mononuclear Nonheme Iron(IV)–Amido Complex Relevant for the Compound II Chemistry of Cytochrome P450.  United States: N. p., 2018. 
Web.  doi:10.1021/jacs.8b11045.

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                    Lu, Xiaoyan, Li, Xiao-Xi, Seo, Mi Sook, Lee, Yong-Min, Clémancey, Martin, Maldivi, Pascale, Latour, Jean-Marc, Sarangi, Ritimukta, Fukuzumi, Shunichi, & Nam, Wonwoo. A Mononuclear Nonheme Iron(IV)–Amido Complex Relevant for the Compound II Chemistry of Cytochrome P450.  United States.  https://doi.org/10.1021/jacs.8b11045

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                    Lu, Xiaoyan, Li, Xiao-Xi, Seo, Mi Sook, Lee, Yong-Min, Clémancey, Martin, Maldivi, Pascale, Latour, Jean-Marc, Sarangi, Ritimukta, Fukuzumi, Shunichi, and Nam, Wonwoo. Sat .  
"A Mononuclear Nonheme Iron(IV)–Amido Complex Relevant for the Compound II Chemistry of Cytochrome P450".  United States.  https://doi.org/10.1021/jacs.8b11045.  https://www.osti.gov/servlets/purl/1493335.

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@article{osti_1493335,

  title        = {A Mononuclear Nonheme Iron(IV)–Amido Complex Relevant for the Compound II Chemistry of Cytochrome P450},

  author       = {Lu, Xiaoyan and Li, Xiao-Xi and Seo, Mi Sook and Lee, Yong-Min and Clémancey, Martin and Maldivi, Pascale and Latour, Jean-Marc and Sarangi, Ritimukta and Fukuzumi, Shunichi and Nam, Wonwoo},

  abstractNote = {A mononuclear nonheme iron(IV)–amido complex bearing a tetraamido macrocyclic ligand, [(TAML)FeIV(NHTs)]- (1), was synthesized via a hydrogen atom (H atom) abstraction reaction of an iron(V)–imido complex, [(TAML)FeV(NTs)]- (2), and fully characterized using various spectroscopies. We then investigated (1) the pKa of 1, (2) the reaction of 1 with a carbon-centered radical, and (3) the H atom abstraction reaction of 1. To the best of our knowledge, the present study reports for the first time the synthesis and chemical properties/reactions of a high-valent iron(IV)–amido complex.},

  doi          = {10.1021/jacs.8b11045},

  journal      = {Journal of the American Chemical Society},

  number       = 1,

  volume       = 141,

  place        = {United States},

  year         = {Sat Nov 24 00:00:00 EST 2018},

  month        = {Sat Nov 24 00:00:00 EST 2018}

}

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Works referenced in this record:

Oxygen Activation and Radical Transformations in Heme Proteins and Metalloporphyrins
journal, December 2017

Huang, Xiongyi; Groves, John T.
Chemical Reviews, Vol. 118, Issue 5
DOI: 10.1021/acs.chemrev.7b00373

A new look at the role of thiolate ligation in cytochrome P450
journal, January 2017

Yosca, Timothy H.; Ledray, Aaron P.; Ngo, Joanna
JBIC Journal of Biological Inorganic Chemistry, Vol. 22, Issue 2-3
DOI: 10.1007/s00775-016-1430-3

Preparation of Compound I in P450 _cam : The Prototypical P450
journal, July 2016

Yosca, Timothy H.; Green, Michael T.
Israel Journal of Chemistry, Vol. 56, Issue 9-10
DOI: 10.1002/ijch.201600013

Hydrocarbon Hydroxylation by Cytochrome P450 Enzymes
journal, February 2010

Ortiz de Montellano, Paul R.
Chemical Reviews, Vol. 110, Issue 2
DOI: 10.1021/cr9002193

P450 Enzymes: Their Structure, Reactivity, and Selectivity—Modeled by QM/MM Calculations
journal, February 2010

Shaik, Sason; Cohen, Shimrit; Wang, Yong
Chemical Reviews, Vol. 110, Issue 2
DOI: 10.1021/cr900121s

O ₂ Activation by Non-Heme Iron Enzymes
journal, November 2016

Solomon, Edward I.; Goudarzi, Serra; Sutherlin, Kyle D.
Biochemistry, Vol. 55, Issue 46
DOI: 10.1021/acs.biochem.6b00635

Dioxygen activation by nonheme iron enzymes with the 2-His-1-carboxylate facial triad that generate high-valent oxoiron oxidants
journal, January 2017

Kal, Subhasree; Que, Lawrence
JBIC Journal of Biological Inorganic Chemistry, Vol. 22, Issue 2-3
DOI: 10.1007/s00775-016-1431-2

Hydrogen Atom Transfer Reactions of Mononuclear Nonheme Metal–Oxygen Intermediates
journal, August 2018

Nam, Wonwoo; Lee, Yong-Min; Fukuzumi, Shunichi
Accounts of Chemical Research, Vol. 51, Issue 9
DOI: 10.1021/acs.accounts.8b00299

Oxidation Reactions with Bioinspired Mononuclear Non-Heme Metal-Oxo Complexes
journal, June 2016

Engelmann, Xenia; Monte-Pérez, Inés; Ray, Kallol
Angewandte Chemie International Edition, Vol. 55, Issue 27
DOI: 10.1002/anie.201600507

Toward the Synthesis of More Reactive S = 2 Non-Heme Oxoiron(IV) Complexes
journal, July 2015

Puri, Mayank; Que, Lawrence
Accounts of Chemical Research, Vol. 48, Issue 8
DOI: 10.1021/acs.accounts.5b00244

Molecular Designs for Controlling the Local Environments around Metal Ions
journal, July 2015

Cook, Sarah A.; Borovik, A. S.
Accounts of Chemical Research, Vol. 48, Issue 8
DOI: 10.1021/acs.accounts.5b00212

Tuning Reactivity and Mechanism in Oxidation Reactions by Mononuclear Nonheme Iron(IV)-Oxo Complexes
journal, February 2014

Nam, Wonwoo; Lee, Yong-Min; Fukuzumi, Shunichi
Accounts of Chemical Research, Vol. 47, Issue 4
DOI: 10.1021/ar400258p

Beyond ferryl-mediated hydroxylation: 40 years of the rebound mechanism and C–H activation
journal, December 2016

Huang, Xiongyi; Groves, John T.
JBIC Journal of Biological Inorganic Chemistry, Vol. 22, Issue 2-3
DOI: 10.1007/s00775-016-1414-3

To rebound or dissociate? This is the mechanistic question in C–H hydroxylation by heme and nonheme metal–oxo complexes
journal, January 2016

Cho, Kyung-Bin; Hirao, Hajime; Shaik, Sason
Chemical Society Reviews, Vol. 45, Issue 5
DOI: 10.1039/C5CS00566C

Direct Observation of Oxygen Rebound with an Iron-Hydroxide Complex
journal, September 2017

Zaragoza, Jan Paulo T.; Yosca, Timothy H.; Siegler, Maxime A.
Journal of the American Chemical Society, Vol. 139, Issue 39
DOI: 10.1021/jacs.7b07979

Observation of Radical Rebound in a Mononuclear Nonheme Iron Model Complex
journal, February 2018

Pangia, Thomas M.; Davies, Casey G.; Prendergast, Joshua R.
Journal of the American Chemical Society, Vol. 140, Issue 12
DOI: 10.1021/jacs.7b12707

Oxoiron(IV) in Chloroperoxidase Compound II Is Basic: Implications for P450 Chemistry
journal, June 2004

Green, M. T.
Science, Vol. 304, Issue 5677
DOI: 10.1126/science.1096897

Iron(IV)hydroxide pKa and the Role of Thiolate Ligation in C-H Bond Activation by Cytochrome P450
journal, November 2013

Yosca, T. H.; Rittle, J.; Krest, C. M.
Science, Vol. 342, Issue 6160
DOI: 10.1126/science.1244373

Significantly shorter Fe–S bond in cytochrome P450-I is consistent with greater reactivity relative to chloroperoxidase
journal, August 2015

Krest, Courtney M.; Silakov, Alexey; Rittle, Jonathan
Nature Chemistry, Vol. 7, Issue 9
DOI: 10.1038/nchem.2306

Characterization of a selenocysteine-ligated P450 compound I reveals direct link between electron donation and reactivity
journal, May 2017

Onderko, Elizabeth L.; Silakov, Alexey; Yosca, Timothy H.
Nature Chemistry, Vol. 9, Issue 7
DOI: 10.1038/nchem.2781

Spectroscopic Investigations of Catalase Compound II: Characterization of an Iron(IV) Hydroxide Intermediate in a Non-thiolate-Ligated Heme Enzyme
journal, November 2016

Yosca, Timothy H.; Langston, Matthew C.; Krest, Courtney M.
Journal of the American Chemical Society, Vol. 138, Issue 49
DOI: 10.1021/jacs.6b09693

Heme-thiolate ferryl of aromatic peroxygenase is basic and reactive
journal, March 2015

Wang, Xiaoshi; Ullrich, René; Hofrichter, Martin
Proceedings of the National Academy of Sciences
DOI: 10.1073/pnas.1503340112

Selective functionalisation of saturated C–H bonds with metalloporphyrin catalysts
journal, January 2011

Che, Chi-Ming; Lo, Vanessa Kar-Yan; Zhou, Cong-Ying
Chemical Society Reviews, Vol. 40, Issue 4
DOI: 10.1039/c0cs00142b

ME and ME complexes of iron and cobalt that emphasize three-fold symmetry (E=O, N, NR)
journal, April 2011

Saouma, Caroline T.; Peters, Jonas C.
Coordination Chemistry Reviews, Vol. 255, Issue 7-8
DOI: 10.1016/j.ccr.2011.01.009

Nitrido and imido transition metal complexes of Groups 6–8
journal, August 2003

Eikey, R.
Coordination Chemistry Reviews, Vol. 243, Issue 1-2
DOI: 10.1016/S0010-8545(03)00048-1

Terminal Nitrido and Imido Complexes of the late Transition Metals
journal, March 2009

Berry, John F.
Comments on Inorganic Chemistry, Vol. 30, Issue 1-2
DOI: 10.1080/02603590902768875

C-H bond amination by iron-imido/nitrene species
journal, April 2012

Zhang, Long; Deng, Liang
Chinese Science Bulletin, Vol. 57, Issue 19
DOI: 10.1007/s11434-012-5151-x

A Mononuclear Nonheme Iron(V)-Imido Complex
journal, June 2017

Hong, Seungwoo; Sutherlin, Kyle D.; Vardhaman, Anil Kumar
Journal of the American Chemical Society, Vol. 139, Issue 26
DOI: 10.1021/jacs.7b04695

Achieving One-Electron Oxidation of a Mononuclear Nonheme Iron(V)-Imido Complex
journal, October 2017

Hong, Seungwoo; Lu, Xiaoyan; Lee, Yong-Min
Journal of the American Chemical Society, Vol. 139, Issue 41
DOI: 10.1021/jacs.7b08161

High valent transition metal chemistry. Synthesis and characterization of an intermediate-spin iron(IV) complex of a strong .pi.-acid ligand
journal, October 1992

Collins, Terrence J.; Fox, Brian G.; Hu, Zheng Guo
Journal of the American Chemical Society, Vol. 114, Issue 22
DOI: 10.1021/ja00048a069

X-ray absorption near-edge spectroscopy in bioinorganic chemistry: Application to M–O2 systems
journal, January 2013

Sarangi, Ritimukta
Coordination Chemistry Reviews, Vol. 257, Issue 2
DOI: 10.1016/j.ccr.2012.06.024

A Multiplet Analysis of Fe K-Edge 1s → 3d Pre-Edge Features of Iron Complexes
journal, July 1997

Westre, Tami E.; Kennepohl, Pierre; DeWitt, Jane G.
Journal of the American Chemical Society, Vol. 119, Issue 27
DOI: 10.1021/ja964352a

Elimination Mechanisms in the Aminolysis of Sulfamate Esters of the Type NH ₂ SO ₂ OC ₆ H ₄ X - Models of Enzyme Inhibitors
journal, August 2008

Spillane, William J.; O'Byrne, Andrew; McCaw, Cheryl J. A.
European Journal of Organic Chemistry, Vol. 2008, Issue 24
DOI: 10.1002/ejoc.200800366

Kinetics and Mechanism of Oxidation Reactions of Porphyrin−Iron(IV)−Oxo Intermediates
journal, August 2007

Pan, Zhengzheng; Newcomb, Martin
Inorganic Chemistry, Vol. 46, Issue 16
DOI: 10.1021/ic700395j

Acid-catalyzed disproportionation of oxoiron(IV) porphyrins to give oxoiron(IV) porphyrin radical cations
journal, June 2011

Pan, Zhengzheng; Newcomb, Martin
Inorganic Chemistry Communications, Vol. 14, Issue 6
DOI: 10.1016/j.inoche.2011.03.044

Hydrogen Atom Abstraction by Metal−Oxo Complexes: Understanding the Analogy with Organic Radical Reactions
journal, August 1998

Mayer, James M.
Accounts of Chemical Research, Vol. 31, Issue 8
DOI: 10.1021/ar970171h

C-H bond activation in heme proteins: the role of thiolate ligation in cytochrome P450
journal, February 2009

Green, Michael T.
Current Opinion in Chemical Biology, Vol. 13, Issue 1, p. 84-88
DOI: 10.1016/j.cbpa.2009.02.028

Thermochemistry of Proton-Coupled Electron Transfer Reagents and its Implications
journal, December 2010

Warren, Jeffrey J.; Tronic, Tristan A.; Mayer, James M.
Chemical Reviews, Vol. 110, Issue 12
DOI: 10.1021/cr100085k

Thermodynamics of Hydrogen Atom Transfer to a High-Valent Iron Imido Complex
journal, March 2008

Nieto, Ismael; Ding, Feizhi; Bontchev, Ranko P.
Journal of the American Chemical Society, Vol. 130, Issue 9
DOI: 10.1021/ja0776834

The triphenylmethyl radical: equilibrium measurements and the reaction with thiophenol
journal, June 1978

Colle, Thomas H.; Glaspie, P. Scott; Lewis, Edward S.
The Journal of Organic Chemistry, Vol. 43, Issue 13
DOI: 10.1021/jo00407a046

Copper(II) Anilides in sp ³ C-H Amination
journal, July 2014

Jang, Eun Sil; McMullin, Claire L.; Käß, Martina
Journal of the American Chemical Society, Vol. 136, Issue 31
DOI: 10.1021/ja5026547

Characterization of Iron-Imido Species Relevant for N -Group Transfer Chemistry
journal, February 2016

Iovan, Diana A.; Betley, Theodore A.
Journal of the American Chemical Society, Vol. 138, Issue 6
DOI: 10.1021/jacs.5b12582

Works referencing / citing this record:

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A designed second-sphere hydrogen-bond interaction that critically influences the O–O bond activation for heterolytic cleavage in ferric iron–porphyrin complexes
journal, January 2020

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Title: A Mononuclear Nonheme Iron(IV)–Amido Complex Relevant for the Compound II Chemistry of Cytochrome P450

Abstract

Citation Formats

Oxygen Activation and Radical Transformations in Heme Proteins and Metalloporphyrins journal, December 2017

A new look at the role of thiolate ligation in cytochrome P450 journal, January 2017

Preparation of Compound I in P450 cam : The Prototypical P450 journal, July 2016

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Hydrogen Atom Transfer Reactions of Mononuclear Nonheme Metal–Oxygen Intermediates journal, August 2018

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Beyond ferryl-mediated hydroxylation: 40 years of the rebound mechanism and C–H activation journal, December 2016

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Direct Observation of Oxygen Rebound with an Iron-Hydroxide Complex journal, September 2017

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Spectroscopic Investigations of Catalase Compound II: Characterization of an Iron(IV) Hydroxide Intermediate in a Non-thiolate-Ligated Heme Enzyme journal, November 2016

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A Multiplet Analysis of Fe K-Edge 1s → 3d Pre-Edge Features of Iron Complexes journal, July 1997

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A new look at the role of thiolate ligation in cytochrome P450
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P450 Enzymes: Their Structure, Reactivity, and Selectivity—Modeled by QM/MM Calculations
journal, February 2010

O ₂ Activation by Non-Heme Iron Enzymes
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Dioxygen activation by nonheme iron enzymes with the 2-His-1-carboxylate facial triad that generate high-valent oxoiron oxidants
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journal, December 2016

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journal, January 2016

Direct Observation of Oxygen Rebound with an Iron-Hydroxide Complex
journal, September 2017

Observation of Radical Rebound in a Mononuclear Nonheme Iron Model Complex
journal, February 2018

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Significantly shorter Fe–S bond in cytochrome P450-I is consistent with greater reactivity relative to chloroperoxidase
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Characterization of a selenocysteine-ligated P450 compound I reveals direct link between electron donation and reactivity
journal, May 2017

Spectroscopic Investigations of Catalase Compound II: Characterization of an Iron(IV) Hydroxide Intermediate in a Non-thiolate-Ligated Heme Enzyme
journal, November 2016

Heme-thiolate ferryl of aromatic peroxygenase is basic and reactive
journal, March 2015

Selective functionalisation of saturated C–H bonds with metalloporphyrin catalysts
journal, January 2011

ME and ME complexes of iron and cobalt that emphasize three-fold symmetry (E=O, N, NR)
journal, April 2011

Nitrido and imido transition metal complexes of Groups 6–8
journal, August 2003

Terminal Nitrido and Imido Complexes of the late Transition Metals
journal, March 2009

C-H bond amination by iron-imido/nitrene species
journal, April 2012

A Mononuclear Nonheme Iron(V)-Imido Complex
journal, June 2017

Achieving One-Electron Oxidation of a Mononuclear Nonheme Iron(V)-Imido Complex
journal, October 2017

High valent transition metal chemistry. Synthesis and characterization of an intermediate-spin iron(IV) complex of a strong .pi.-acid ligand
journal, October 1992

X-ray absorption near-edge spectroscopy in bioinorganic chemistry: Application to M–O2 systems
journal, January 2013

A Multiplet Analysis of Fe K-Edge 1s → 3d Pre-Edge Features of Iron Complexes
journal, July 1997

Elimination Mechanisms in the Aminolysis of Sulfamate Esters of the Type NH ₂ SO ₂ OC ₆ H ₄ X - Models of Enzyme Inhibitors
journal, August 2008

Kinetics and Mechanism of Oxidation Reactions of Porphyrin−Iron(IV)−Oxo Intermediates
journal, August 2007

Acid-catalyzed disproportionation of oxoiron(IV) porphyrins to give oxoiron(IV) porphyrin radical cations
journal, June 2011

Hydrogen Atom Abstraction by Metal−Oxo Complexes: Understanding the Analogy with Organic Radical Reactions
journal, August 1998

C-H bond activation in heme proteins: the role of thiolate ligation in cytochrome P450
journal, February 2009

Thermochemistry of Proton-Coupled Electron Transfer Reagents and its Implications
journal, December 2010

Thermodynamics of Hydrogen Atom Transfer to a High-Valent Iron Imido Complex
journal, March 2008

The triphenylmethyl radical: equilibrium measurements and the reaction with thiophenol
journal, June 1978

Copper(II) Anilides in sp ³ C-H Amination
journal, July 2014

Characterization of Iron-Imido Species Relevant for N -Group Transfer Chemistry
journal, February 2016

Octahedral iron( iv )–tosylimido complexes exhibiting single electron-oxidation reactivity
journal, January 2019

A designed second-sphere hydrogen-bond interaction that critically influences the O–O bond activation for heterolytic cleavage in ferric iron–porphyrin complexes
journal, January 2020