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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:
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  1. UCB
  2. (
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
Resource Relation:
Journal Name: Nat. Chem.; 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 = {Tue Aug 19 00:00:00 EDT 2014},
month = {Tue Aug 19 00:00:00 EDT 2014}
}