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Title: Accelerated Oxygen Atom Transfer and C-H Bond Oxygenation by Remote Redox Changes in Fe 3Mn-Iodosobenzene Adducts

Abstract

In this paper, we report the synthesis, characterization, and reactivity of [LFe 3(PhPz) 3OMn( sPhIO)][OTf] x (3: x=2; 4: x=3), where 4 is one of very few examples of iodosobenzene–metal adducts characterized by X-ray crystallography. Access to these rare heterometallic clusters enabled differentiation of the metal centers involved in oxygen atom transfer (Mn) or redox modulation (Fe). Specifically, 57Fe Mössbauer and X-ray absorption spectroscopy provided unique insights into how changes in oxidation state (Fe III 2Fe IIMn II vs. Fe III 3Mn II) influence oxygen atom transfer in tetranuclear Fe 3Mn clusters. Finally, in particular, a one-electron redox change at a distal metal site leads to a change in oxygen atom transfer reactivity by ca. two orders of magnitude.

Authors:
 [1];  [1];  [2];  [2];  [1];  [1];  [2]; ORCiD logo [1]
  1. California Inst. of Technology (CalTech), Pasadena, CA (United States)
  2. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); National Inst. of Health (NIH) (United States)
OSTI Identifier:
1379810
Alternate Identifier(s):
OSTI ID: 1401528
Grant/Contract Number:  
AC02-05CH11231; R01-GM102687B; DEAC02- 05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
Angewandte Chemie (International Edition)
Additional Journal Information:
Journal Name: Angewandte Chemie (International Edition); Journal Volume: 56; Journal Issue: 17; Journal ID: ISSN 1433-7851
Publisher:
Wiley
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; C-H bond oxygenation; clusters; iodosobenzene adduct; multimetallic complexes; oxygen atom transfer

Citation Formats

de Ruiter, Graham, Carsch, Kurtis M., Gul, Sheraz, Chatterjee, Ruchira, Thompson, Niklas B., Takase, Michael K., Yano, Junko, and Agapie, Theodor. Accelerated Oxygen Atom Transfer and C-H Bond Oxygenation by Remote Redox Changes in Fe3Mn-Iodosobenzene Adducts. United States: N. p., 2017. Web. doi:10.1002/anie.201701319.
de Ruiter, Graham, Carsch, Kurtis M., Gul, Sheraz, Chatterjee, Ruchira, Thompson, Niklas B., Takase, Michael K., Yano, Junko, & Agapie, Theodor. Accelerated Oxygen Atom Transfer and C-H Bond Oxygenation by Remote Redox Changes in Fe3Mn-Iodosobenzene Adducts. United States. doi:10.1002/anie.201701319.
de Ruiter, Graham, Carsch, Kurtis M., Gul, Sheraz, Chatterjee, Ruchira, Thompson, Niklas B., Takase, Michael K., Yano, Junko, and Agapie, Theodor. Fri . "Accelerated Oxygen Atom Transfer and C-H Bond Oxygenation by Remote Redox Changes in Fe3Mn-Iodosobenzene Adducts". United States. doi:10.1002/anie.201701319. https://www.osti.gov/servlets/purl/1379810.
@article{osti_1379810,
title = {Accelerated Oxygen Atom Transfer and C-H Bond Oxygenation by Remote Redox Changes in Fe3Mn-Iodosobenzene Adducts},
author = {de Ruiter, Graham and Carsch, Kurtis M. and Gul, Sheraz and Chatterjee, Ruchira and Thompson, Niklas B. and Takase, Michael K. and Yano, Junko and Agapie, Theodor},
abstractNote = {In this paper, we report the synthesis, characterization, and reactivity of [LFe3(PhPz)3OMn(sPhIO)][OTf]x (3: x=2; 4: x=3), where 4 is one of very few examples of iodosobenzene–metal adducts characterized by X-ray crystallography. Access to these rare heterometallic clusters enabled differentiation of the metal centers involved in oxygen atom transfer (Mn) or redox modulation (Fe). Specifically, 57Fe Mössbauer and X-ray absorption spectroscopy provided unique insights into how changes in oxidation state (FeIII2FeIIMnII vs. FeIII3MnII) influence oxygen atom transfer in tetranuclear Fe3Mn clusters. Finally, in particular, a one-electron redox change at a distal metal site leads to a change in oxygen atom transfer reactivity by ca. two orders of magnitude.},
doi = {10.1002/anie.201701319},
journal = {Angewandte Chemie (International Edition)},
number = 17,
volume = 56,
place = {United States},
year = {2017},
month = {3}
}

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Cited by: 6 works
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Figures / Tables:

Figure 1 Figure 1: General molecular structure of [LFe3(PhPz)3OMn]n+ 3 (n = 2–3; top left), supported by pyrazolates and a 1,3,5- triarylbenzene-based ligand. The inset shows the coloring scheme for the metal oxidation states.

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  • Angewandte Chemie International Edition, Vol. 56, Issue 17
  • DOI: 10.1002/anie.201701319

    Works referencing / citing this record:

    Charakterisierung eines Oxo(porphyrinato)-mangan(IV)-Komplexes mit Röntgenabsorptionsspektroskopie
    journal, February 1995


    An Iron(III) Iodosylbenzene Complex: A Masked Non-Heme Fe V O
    journal, May 2012

    • Lennartson, Anders; McKenzie, Christine J.
    • Angewandte Chemie, Vol. 124, Issue 27
    • DOI: 10.1002/ange.201202487

    Structure and Reactivity of an Iodosylarene Adduct of a Manganese(IV)-Salen Complex
    journal, June 2012

    • Wang, Chunlan; Kurahashi, Takuya; Fujii, Hiroshi
    • Angewandte Chemie, Vol. 124, Issue 31
    • DOI: 10.1002/ange.201202835

    Highly Reactive Nonheme Iron(III) Iodosylarene Complexes in Alkane Hydroxylation and Sulfoxidation Reactions
    journal, May 2014


    Characterization of an Oxo(porphyrinato)manganese(IV) Complex by X-ray Absorption Spectroscopy
    journal, February 1995

    • Charnock, John M.; Garner, C. David; Trautwein, Alfred X.
    • Angewandte Chemie International Edition in English, Vol. 34, Issue 3
    • DOI: 10.1002/anie.199503431

    An Iron(III) Iodosylbenzene Complex: A Masked Non-Heme Fe V O
    journal, May 2012

    • Lennartson, Anders; McKenzie, Christine J.
    • Angewandte Chemie International Edition, Vol. 51, Issue 27
    • DOI: 10.1002/anie.201202487

    Structure and Reactivity of an Iodosylarene Adduct of a Manganese(IV)-Salen Complex
    journal, June 2012

    • Wang, Chunlan; Kurahashi, Takuya; Fujii, Hiroshi
    • Angewandte Chemie International Edition, Vol. 51, Issue 31
    • DOI: 10.1002/anie.201202835

    Highly Reactive Nonheme Iron(III) Iodosylarene Complexes in Alkane Hydroxylation and Sulfoxidation Reactions
    journal, May 2014

    • Hong, Seungwoo; Wang, Bin; Seo, Mi Sook
    • Angewandte Chemie International Edition, Vol. 53, Issue 25
    • DOI: 10.1002/anie.201402537

    Hydrogen-Atom Abstraction Reactions by Manganese(V)- and Manganese(IV)-Oxo Porphyrin Complexes in Aqueous Solution
    journal, October 2009

    • Arunkumar, Chellaiah; Lee, Yong-Min; Lee, Jung Yoon
    • Chemistry - A European Journal, Vol. 15, Issue 43
    • DOI: 10.1002/chem.200901362

    Selectivity of C−H versus C−F Bond Oxygenation by Homo- and Heterometallic Fe 4 , Fe 3 Mn, and Mn 4 Clusters
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    journal, March 2011

    • Latifi, Reza; Tahsini, Laleh; Karamzadeh, Baharan
    • Archives of Biochemistry and Biophysics, Vol. 507, Issue 1
    • DOI: 10.1016/j.abb.2010.12.035

    High-valent nonheme iron-oxo complexes: Synthesis, structure, and spectroscopy
    journal, January 2013


    A rare mixed-valence state manganese(II/IV) tetranuclear cage formed using phenyl 2-pyridyl ketone oxime and azide as ligands
    journal, June 2006

    • Milios, Constantinos J.; Piligkos, Stergios; Bell, Aidan R.
    • Inorganic Chemistry Communications, Vol. 9, Issue 6
    • DOI: 10.1016/j.inoche.2006.03.013

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


    Synthetic Mononuclear Nonheme Iron–Oxygen Intermediates
    journal, July 2015


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


    A Balancing Act: Stability versus Reactivity of Mn(O) Complexes
    journal, September 2015


    A Theory for Bioinorganic Chemical Reactivity of Oxometal Complexes and Analogous Oxidants: The Exchange and Orbital-Selection Rules
    journal, December 2012

    • Usharani, Dandamudi; Janardanan, Deepa; Li, Chunsen
    • Accounts of Chemical Research, Vol. 46, Issue 2
    • DOI: 10.1021/ar300204y

    Non-Heme Fe(IV)–Oxo Intermediates
    journal, July 2007

    • Krebs, Carsten; Galonić Fujimori, Danica; Walsh, Christopher T.
    • Accounts of Chemical Research, Vol. 40, Issue 7
    • DOI: 10.1021/ar700066p

    Dioxygen Activation at Mononuclear Nonheme Iron Active Sites:  Enzymes, Models, and Intermediates
    journal, February 2004

    • Costas, Miquel; Mehn, Mark P.; Jensen, Michael P.
    • Chemical Reviews, Vol. 104, Issue 2
    • DOI: 10.1021/cr020628n

    Mn 4 Ca Cluster in Photosynthesis: Where and How Water is Oxidized to Dioxygen
    journal, March 2014

    • Yano, Junko; Yachandra, Vittal
    • Chemical Reviews, Vol. 114, Issue 8
    • DOI: 10.1021/cr4004874

    Synthetic Cluster Models of Biological and Heterogeneous Manganese Catalysts for O 2 Evolution
    journal, December 2013

    • Tsui, Emily Y.; Kanady, Jacob S.; Agapie, Theodor
    • Inorganic Chemistry, Vol. 52, Issue 24
    • DOI: 10.1021/ic402236f

    Multiple Active Oxidants in Cytochrome P-450 Model Oxidations
    journal, November 2000

    • Collman, James P.; Chien, Allis S.; Eberspacher, Todd A.
    • Journal of the American Chemical Society, Vol. 122, Issue 45
    • DOI: 10.1021/ja000961d

    Synthesis, characterization, and reactivity of oxomanganese(IV) porphyrin complexes
    journal, December 1988

    • Groves, John T.; Stern, Michael K.
    • Journal of the American Chemical Society, Vol. 110, Issue 26
    • DOI: 10.1021/ja00234a009

    High-valent iron-porphyrin complexes related to peroxidase and cytochrome P-450
    journal, May 1981

    • Groves, John T.; Haushalter, Robert C.; Nakamura, Mikio
    • Journal of the American Chemical Society, Vol. 103, Issue 10
    • DOI: 10.1021/ja00400a075

    Two-State Reactivity in Alkane Hydroxylation by Non-Heme Iron−Oxo Complexes
    journal, June 2006

    • Hirao, Hajime; Kumar, Devesh; Que, Lawrence
    • Journal of the American Chemical Society, Vol. 128, Issue 26
    • DOI: 10.1021/ja061609o

    A Manganese(V)–Oxo π-Cation Radical Complex: Influence of One-Electron Oxidation on Oxygen-Atom Transfer
    journal, October 2011

    • Prokop, Katharine A.; Neu, Heather M.; de Visser, Sam P.
    • Journal of the American Chemical Society, Vol. 133, Issue 40
    • DOI: 10.1021/ja2066237

    Preparation and Properties of a Monomeric High-Spin Mn V –Oxo Complex
    journal, January 2012

    • Taguchi, Taketo; Gupta, Rupal; Lassalle-Kaiser, Benedikt
    • Journal of the American Chemical Society, Vol. 134, Issue 4
    • DOI: 10.1021/ja210957u

    Secondary Coordination Sphere Influence on the Reactivity of Nonheme Iron(II) Complexes: An Experimental and DFT Approach
    journal, July 2013

    • Sahu, Sumit; Widger, Leland R.; Quesne, Matthew G.
    • Journal of the American Chemical Society, Vol. 135, Issue 29
    • DOI: 10.1021/ja402688t

    Dichotomous Hydrogen Atom Transfer vs Proton-Coupled Electron Transfer During Activation of X–H Bonds (X = C, N, O) by Nonheme Iron–Oxo Complexes of Variable Basicity
    journal, October 2013

    • Usharani, Dandamudi; Lacy, David C.; Borovik, A. S.
    • Journal of the American Chemical Society, Vol. 135, Issue 45
    • DOI: 10.1021/ja408073m

    Heterometallic Triiron-Oxo/Hydroxo Clusters: Effect of Redox-Inactive Metals
    journal, December 2013

    • Herbert, David E.; Lionetti, Davide; Rittle, Jonathan
    • Journal of the American Chemical Society, Vol. 135, Issue 51
    • DOI: 10.1021/ja4104974

    Ferryl Protonation in Oxoiron(IV) Porphyrins and Its Role in Oxygen Transfer
    journal, February 2015

    • Boaz, Nicholas C.; Bell, Seth R.; Groves, John T.
    • Journal of the American Chemical Society, Vol. 137, Issue 8
    • DOI: 10.1021/ja508759t

    Catalytic Reactivity of a Meso -N-Substituted Corrole and Evidence for a High-Valent Iron−Oxo Species
    journal, June 2009

    • McGown, Amanda J.; Kerber, William D.; Fujii, Hiroshi
    • Journal of the American Chemical Society, Vol. 131, Issue 23
    • DOI: 10.1021/ja809183z

    C−H Bond Cleavage with Reductants: Re-Investigating the Reactivity of Monomeric Mn III/IV −Oxo Complexes and the Role of Oxo Ligand Basicity
    journal, March 2009

    • Parsell, Trenton H.; Yang, Meng-Yin; Borovik, A. S.
    • Journal of the American Chemical Society, Vol. 131, Issue 8
    • DOI: 10.1021/ja8100825

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      Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.