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

Abstract

Enzymatic heme and non-heme high-valent iron-oxo species are known to activate strong C–H bonds with relative ease, yet duplicating this reactivity in a synthetic system remains a formidable challenge. While the 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, while nature’s non-heme iron(IV)-oxos possess high-spin S = 2 ground states, this electronic configuration has proven difficult to achieve in a molecular species. These challenges may be mitigated within metal-organic frameworks featuring site-isolated iron centers in a constrained, weak-field ligand environment. As a result, we show that the metal-organic framework Fe 2(dobdc) and its magnesium-diluted analogue, Fe 0.1Mg 1.9(dobdc), are able to convert ethane into ethanol and acetaldehyde using nitrous oxide as the terminal oxidant. Electronic structure calculations indicate that the active oxidant is likely a high-spin S = 2 iron(IV)-oxo species.

Authors:
 [1];  [1];  [1];  [2];  [3];  [4];  [4];  [4];  [4]; ORCiD logo [2];  [5];  [5];  [2];  [5];  [4];  [4];  [6];  [7]
  1. Univ. of California, Berkeley, CA (United States)
  2. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  3. National Inst. of Standards and Technology (NIST), Gaithersburg, MD (United States)
  4. Univ. of Minnesota, Minneapolis, MN (United States)
  5. Univ. of Turin, Torino (Italy)
  6. National Inst. of Standards and Technology (NIST), Gaithersburg, MD (United States); Univ. of Delaware, Newark, DE (United States)
  7. Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Publication Date:
Research Org.:
Univ. of Minnesota, Minneapolis, MN (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division
OSTI Identifier:
1458980
Grant/Contract Number:  
FG02-12ER16362; SC0008688
Resource Type:
Accepted Manuscript
Journal Name:
Nature Chemistry
Additional Journal Information:
Journal Volume: 6; Journal Issue: 7; Journal ID: ISSN 1755-4330
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

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, Crocella, Valentina, Yano, Junko, Bordiga, Silvia, Truhlar, Donald G., Gagliardi, Laura, Brown, Craig M., and Long, Jeffrey R. Oxidation of ethane to ethanol by N2O in a metal–organic framework with coordinatively unsaturated iron(II) sites [Oxidation of ethane to ethanol by nitrous oxide 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, Crocella, Valentina, Yano, Junko, Bordiga, Silvia, Truhlar, Donald G., Gagliardi, Laura, Brown, Craig M., & Long, Jeffrey R. Oxidation of ethane to ethanol by N2O in a metal–organic framework with coordinatively unsaturated iron(II) sites [Oxidation of ethane to ethanol by nitrous oxide 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, Crocella, Valentina, Yano, Junko, Bordiga, Silvia, Truhlar, Donald G., Gagliardi, Laura, Brown, Craig M., and Long, Jeffrey R. Sun . "Oxidation of ethane to ethanol by N2O in a metal–organic framework with coordinatively unsaturated iron(II) sites [Oxidation of ethane to ethanol by nitrous oxide in a metal–organic framework with coordinatively unsaturated iron(II) sites]". United States. doi:10.1038/nchem.1956. https://www.osti.gov/servlets/purl/1458980.
@article{osti_1458980,
title = {Oxidation of ethane to ethanol by N2O in a metal–organic framework with coordinatively unsaturated iron(II) sites [Oxidation of ethane to ethanol by nitrous oxide 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 Crocella, Valentina and Yano, Junko and Bordiga, Silvia and Truhlar, Donald G. and Gagliardi, Laura and Brown, Craig M. and Long, Jeffrey R.},
abstractNote = {Enzymatic heme and non-heme high-valent iron-oxo species are known to activate strong C–H bonds with relative ease, yet duplicating this reactivity in a synthetic system remains a formidable challenge. While the 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, while nature’s non-heme iron(IV)-oxos possess high-spin S = 2 ground states, this electronic configuration has proven difficult to achieve in a molecular species. These challenges may be mitigated within metal-organic frameworks featuring site-isolated iron centers in a constrained, weak-field ligand environment. As a result, we show that the metal-organic framework Fe2(dobdc) and its magnesium-diluted analogue, Fe0.1Mg1.9(dobdc), are able to convert ethane into ethanol and acetaldehyde using nitrous oxide as the terminal oxidant. Electronic structure calculations indicate that the active oxidant is likely a high-spin S = 2 iron(IV)-oxo species.},
doi = {10.1038/nchem.1956},
journal = {Nature Chemistry},
number = 7,
volume = 6,
place = {United States},
year = {2014},
month = {5}
}

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    Works referencing / citing this record:

    CCDC 977093: Experimental Crystal Structure Determination: WOPSAX02 : catena-((μ8-2,5-Dioxyterephthalato)-di-iron nitrous oxide)
    dataset, April 2014

    • Xiao, Dianne; Bloch, Eric; Mason, Jarad
    • Cambridge Structural Database (CSD)
    • DOI: 10.5517/cc11sr4q

    CCDC 977094: Experimental Crystal Structure Determination: WOPSAX01 : catena-((μ8-2,5-Dioxyterephthalato)-di-iron nitrous oxide)
    dataset, April 2014

    • Xiao, Dianne J.; Bloch, Eric D.; Mason, Jarad A.
    • Cambridge Structural Database (CSD)
    • DOI: 10.5517/cc11sr5r

    CCDC 977095: Experimental Crystal Structure Determination: WOPSOL : catena-((μ8-2,5-Dioxyterephthalato)-dihydroxy-di-iron)
    dataset, April 2014

    • Xiao, Dianne J.; Bloch, Eric D.; Mason, Jarad A.
    • Cambridge Structural Database (CSD)
    • DOI: 10.5517/cc11sr6s

    CCDC 977096: Experimental Crystal Structure Determination: WOPSOL01 : catena-((μ8-2,5-Dioxyterephthalato)-dihydroxy-di-iron)
    dataset, April 2014

    • Xiao, Dianne; Bloch, Eric; Mason, Jarad
    • Cambridge Structural Database (CSD)
    • DOI: 10.5517/cc11sr7t