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Title: Oxidation of ethane to ethanol by N 2O in a metal-organic framework with coordinatively unsaturated iron(II) sites

Abstract

Enzymatic haem and non-haem high-valent iron–oxo species are known to activate strong C–H bonds, yet duplicating this reactivity in a synthetic system remains a formidable challenge. Although instability of the terminal iron–oxo moiety is perhaps the foremost obstacle, steric and electronic factors also limit the activity of previously reported mononuclear iron(IV)–oxo compounds. In particular, although nature's non-haem iron(IV)–oxo compounds possess high-spin S = 2 ground states, this electronic configuration has proved difficult to achieve in a molecular species. These challenges may be mitigated within metal–organic frameworks that feature site-isolated iron centres in a constrained, weak-field ligand environment. Here, we show that the metal–organic framework Fe 2(dobdc) (dobdc 4- = 2,5-dioxido-1,4-benzenedicarboxylate) and its magnesium-diluted analogue, Fe 0.1Mg 1.9(dobdc), are able to activate the C–H bonds of ethane and convert it into ethanol and acetaldehyde using nitrous oxide as the terminal oxidant. Electronic structure calculations indicate that the active oxidant is likely to be a high-spin S = 2 iron(IV)–oxo species.

Authors:
; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ;  [1]
  1. UCB
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
Sponsoring Org.:
DOE - BASIC ENERGY SCIENCES
OSTI Identifier:
1140209
Resource Type:
Journal Article
Journal Name:
Nat. Chem.
Additional Journal Information:
Journal Volume: 6; Journal Issue: 2014
Country of Publication:
United States
Language:
ENGLISH

Citation Formats

Xiao, Dianne J., Bloch, Eric D., Mason, Jarad A., Queen, Wendy L., Hudson, Matthew R., Planas, Nora, Borycz, Joshua, Dzubak, Allison L., Verma, Pragya, Lee, Kyuho, Bonino, Francesca, Crocellà, Valentina, Yano, Junko, Bordiga, Silvia, Truhlar, Donald G., Gagliardi, Laura, Brown, Craig M., Long, Jeffrey R., NIST), LBNL), UMM), and Turin). Oxidation of ethane to ethanol by N2O in a metal-organic framework with coordinatively unsaturated iron(II) sites. United States: N. p., 2014. Web. doi:10.1038/nchem.1956.
Xiao, Dianne J., Bloch, Eric D., Mason, Jarad A., Queen, Wendy L., Hudson, Matthew R., Planas, Nora, Borycz, Joshua, Dzubak, Allison L., Verma, Pragya, Lee, Kyuho, Bonino, Francesca, Crocellà, Valentina, Yano, Junko, Bordiga, Silvia, Truhlar, Donald G., Gagliardi, Laura, Brown, Craig M., Long, Jeffrey R., NIST), LBNL), UMM), & Turin). Oxidation of ethane to ethanol by N2O in a metal-organic framework with coordinatively unsaturated iron(II) sites. United States. doi:10.1038/nchem.1956.
Xiao, Dianne J., Bloch, Eric D., Mason, Jarad A., Queen, Wendy L., Hudson, Matthew R., Planas, Nora, Borycz, Joshua, Dzubak, Allison L., Verma, Pragya, Lee, Kyuho, Bonino, Francesca, Crocellà, Valentina, Yano, Junko, Bordiga, Silvia, Truhlar, Donald G., Gagliardi, Laura, Brown, Craig M., Long, Jeffrey R., NIST), LBNL), UMM), and Turin). Tue . "Oxidation of ethane to ethanol by N2O in a metal-organic framework with coordinatively unsaturated iron(II) sites". United States. doi:10.1038/nchem.1956.
@article{osti_1140209,
title = {Oxidation of ethane to ethanol by N2O in a metal-organic framework with coordinatively unsaturated iron(II) sites},
author = {Xiao, Dianne J. and Bloch, Eric D. and Mason, Jarad A. and Queen, Wendy L. and Hudson, Matthew R. and Planas, Nora and Borycz, Joshua and Dzubak, Allison L. and Verma, Pragya and Lee, Kyuho and Bonino, Francesca and Crocellà, Valentina and Yano, Junko and Bordiga, Silvia and Truhlar, Donald G. and Gagliardi, Laura and Brown, Craig M. and Long, Jeffrey R. and NIST) and LBNL) and UMM) and Turin)},
abstractNote = {Enzymatic haem and non-haem high-valent iron–oxo species are known to activate strong C–H bonds, yet duplicating this reactivity in a synthetic system remains a formidable challenge. Although instability of the terminal iron–oxo moiety is perhaps the foremost obstacle, steric and electronic factors also limit the activity of previously reported mononuclear iron(IV)–oxo compounds. In particular, although nature's non-haem iron(IV)–oxo compounds possess high-spin S = 2 ground states, this electronic configuration has proved difficult to achieve in a molecular species. These challenges may be mitigated within metal–organic frameworks that feature site-isolated iron centres in a constrained, weak-field ligand environment. Here, we show that the metal–organic framework Fe2(dobdc) (dobdc4- = 2,5-dioxido-1,4-benzenedicarboxylate) and its magnesium-diluted analogue, Fe0.1Mg1.9(dobdc), are able to activate the C–H bonds of ethane and convert it into ethanol and acetaldehyde using nitrous oxide as the terminal oxidant. Electronic structure calculations indicate that the active oxidant is likely to be a high-spin S = 2 iron(IV)–oxo species.},
doi = {10.1038/nchem.1956},
journal = {Nat. Chem.},
number = 2014,
volume = 6,
place = {United States},
year = {2014},
month = {8}
}

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    • DOI: 10.1021/cr010361c

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    • Meunier, Bernard; de Visser, Samuël P.; Shaik, Sason
    • Chemical Reviews, Vol. 104, Issue 9
    • DOI: 10.1021/cr020443g

    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

    Dioxygen Activation by Enzymes Containing Binuclear Non-Heme Iron Clusters
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    • Wallar, Bradley J.; Lipscomb, John D.
    • Chemical Reviews, Vol. 96, Issue 7
    • DOI: 10.1021/cr9500489

    Hydrogen Atom Abstraction by a Mononuclear Ferric Hydroxide Complex:  Insights into the Reactivity of Lipoxygenase
    journal, July 2006

    • Goldsmith, Christian R.; Stack, T. Daniel P.
    • Inorganic Chemistry, Vol. 45, Issue 15
    • DOI: 10.1021/ic060621e

    Single-Ion Magnetic Anisotropy and Isotropic Magnetic Couplings in the Metal–Organic Framework Fe 2 (dobdc)
    journal, August 2013

    • Maurice, Rémi; Verma, Pragya; Zadrozny, Joseph M.
    • Inorganic Chemistry, Vol. 52, Issue 16
    • DOI: 10.1021/ic400953e

    Mode of bonding of dinitrogen oxide (nitrous oxide) in (dinitrogen oxide)pentaammineruthenium
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    • Bottomley, Frank.; Brooks, Wendell V. F.
    • Inorganic Chemistry, Vol. 16, Issue 2
    • DOI: 10.1021/ic50168a060

    Investigation of Gas Adsorption Performances and H 2 Affinities of Porous Metal-Organic Frameworks with Different Entatic Metal Centers
    journal, June 2009

    • Ma, Shengqian; Yuan, Daqiang; Chang, Jong-San
    • Inorganic Chemistry, Vol. 48, Issue 12
    • DOI: 10.1021/ic900475q

    A Hydrogen-Bond Facilitated Cycle for Oxygen Reduction by an Acid- and Base-Compatible Iron Platform
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    • Inorganic Chemistry, Vol. 48, Issue 21
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    • The Journal of Physical Chemistry, Vol. 94, Issue 14
    • DOI: 10.1021/j100377a012

    Moessbauer-Zeeman spectra of some octaethylporphyrinato- and tetraphenylporphinatoiron(III) complexes
    journal, March 1978

    • Dolphin, David H.; Sams, John R.; Tsin, Tsang Bik
    • Journal of the American Chemical Society, Vol. 100, Issue 6
    • DOI: 10.1021/ja00474a011

    The Nitrous Oxide Complex, RuCl 21 -N 2 O)(P−N)(PPh 3 ) (P−N = [ o -( N,N -Dimethylamino)phenyl]diphenylphosphine); Low Temperature Conversion of N 2 O to N 2 and O 2
    journal, September 2001

    • Pamplin, Craig B.; Ma, Erin S. F.; Safari, Nasser
    • Journal of the American Chemical Society, Vol. 123, Issue 35
    • DOI: 10.1021/ja0106319

    C−H Bond Activation by a Ferric Methoxide Complex:  Modeling the Rate-Determining Step in the Mechanism of Lipoxygenase
    journal, January 2002

    • Goldsmith, Christian R.; Jonas, Robert T.; Stack, T. Daniel P.
    • Journal of the American Chemical Society, Vol. 124, Issue 1
    • DOI: 10.1021/ja016451g

    The Crystal Structure of a High-Spin Oxoiron(IV) Complex and Characterization of Its Self-Decay Pathway
    journal, June 2010

    • England, Jason; Guo, Yisong; Farquhar, Erik R.
    • Journal of the American Chemical Society, Vol. 132, Issue 25
    • DOI: 10.1021/ja100366c

    Formation, Structure, and EPR Detection of a High Spin Fe IV —Oxo Species Derived from Either an Fe III —Oxo or Fe III —OH Complex
    journal, September 2010

    • Lacy, David C.; Gupta, Rupal; Stone, Kari L.
    • Journal of the American Chemical Society, Vol. 132, Issue 35
    • DOI: 10.1021/ja1047818

    A Structurally Characterized Nitrous Oxide Complex of Vanadium
    journal, February 2011

    • Piro, Nicholas A.; Lichterman, Michael F.; Harman, W. Hill
    • Journal of the American Chemical Society, Vol. 133, Issue 7
    • DOI: 10.1021/ja110798w

    A More Reactive Trigonal-Bipyramidal High-Spin Oxoiron(IV) Complex with a cis-Labile Site
    journal, August 2011

    • England, Jason; Guo, Yisong; Van Heuvelen, Katherine M.
    • Journal of the American Chemical Society, Vol. 133, Issue 31
    • DOI: 10.1021/ja2040909

    Selective Binding of O 2 over N 2 in a Redox–Active Metal–Organic Framework with Open Iron(II) Coordination Sites
    journal, September 2011

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    • Journal of the American Chemical Society, Vol. 133, Issue 37
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    A High-Spin Iron(IV)–Oxo Complex Supported by a Trigonal Nonheme Pyrrolide Platform
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    Comprehensive DFT Study of Nitrous Oxide Decomposition over Fe-ZSM-5
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    Room-Temperature Oxidation of Methane by α-Oxygen and Extraction of Products from the FeZSM-5 Surface
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    Adsorption on Fe-MOF-74 for C1–C3 Hydrocarbon Separation
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    C–H activation
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    The biology and chemistry of high-valent iron–oxo and iron–nitrido complexes
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    Ultrathin metal–organic framework nanosheets for electrocatalytic oxygen evolution
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    Structure and nuclearity of active sites in Fe-zeolites: comparison with iron sites in enzymes and homogeneous catalysts
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    Hydrogen storage and carbon dioxide capture in an iron-based sodalite-type metal–organic framework (Fe-BTT) discovered via high-throughput methods
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    N 2 O reduction at a dissymmetric {Cu 2 S}-containing mixed-valent center
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    I 2 -induced SC–SC transformation within two-dimensional Zn( ii )-triazole framework: an ideal detector of cyano-containing molecules
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    Two coordination polymers of benzene-1,2,4,5-tetracarboxylic acid (H 4 BTC): in situ ligand syntheses, structures, and luminescent properties
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    Nitrous oxide activation by a cobalt( ii ) complex for aldehyde oxidation under mild conditions
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    A new transformation of coumarins via direct C–H bond activation utilizing an iron–organic framework as a recyclable catalyst
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    Structural variation of transition metal–organic frameworks using deep eutectic solvents with different hydrogen bond donors
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    Redox-active metal–organic frameworks for energy conversion and storage
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    Second‐order perturbation theory with a complete active space self‐consistent field reference function
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    Anisotropic compressibility of the coordination polymer emim[Mn(btc)]
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    Hydrocarbon Separations in a Metal-Organic Framework with Open Iron(II) Coordination Sites
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    Ethane/ethylene separation in a metal-organic framework with iron-peroxo sites
    journal, October 2018


    Solvothermal Synthesis of Fe-MOF-74 and Its Catalytic Properties in Phenol Hydroxylation
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