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Nat Chem. 2014 Jul;6(7):590-5. doi: 10.1038/nchem.1956. Epub 2014 May 18.

Oxidation of ethane to ethanol by N2O in a metal-organic framework with coordinatively unsaturated iron(II) sites.

Author information

1
Department of Chemistry, University of California, Berkeley, California 94720-1460, USA.
2
The Molecular Foundry, Lawrence Berkeley National Laboratory, Berkeley, California 94720-1460, USA.
3
Center for Neutron Research, National Institute of Standards and Technology, Gaithersburg, Maryland 20899, USA.
4
Department of Chemistry, Chemical Theory Center, and Supercomputing Institute, University of Minnesota, Minneapolis, Minnesota, 55455-0431, USA.
5
Department of Chemistry, NIS and INSTM Reference Centres, University of Turin, I-10135 Torino, Italy.
6
Physical Biosciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720-1460, USA.
7
1] Center for Neutron Research, National Institute of Standards and Technology, Gaithersburg, Maryland 20899, USA [2] Department of Chemical Engineering, University of Delaware, Newark, Delaware 19716, USA.
8
1] Department of Chemistry, University of California, Berkeley, California 94720-1460, USA [2] Materials Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, USA.

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 Fe2(dobdc) (dobdc(4-) = 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.

PMID:
24950328
DOI:
10.1038/nchem.1956
[Indexed for MEDLINE]

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