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

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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) (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.

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Figure 1: Structure of bare and N2O-dosed Fe2(dobdc) (1).
Figure 2: Preparation, spectroscopic characterization and structure of Fe2(OH)2(dobdc).
Figure 3: N2O activation and reactivity of Fe2(dobdc) in the oxidation of ethane and 1,4-cyclohexadiene.
Figure 4: Structure and qualitative MO diagram of Fe2(O)2(dobdc) (4).

Change history

  • 05 June 2014

    In the version of this Article originally published online, in the section 'Oxidation of ethane to give ethanol' the two 1H NMR spectra related to the reaction products resulting from flowing an N2O:ethane:Ar mixture (10:25:65) over Fe2(dobdc) and Fe0.1Mg1.9(dobdc) at 75 °C were not included in the Supplementary Information. These spectra have now been added as Supplementary Figs 21 and 22, respectively, and the Article amended to include appropriate citations to them. The authors have also added a sentence into the Acknowledgements: "Use of the Advanced Photon Source, an Office of Science User Facility operated for the US Department of Energy (DOE) Office of Science by Argonne National Laboratory, was supported by the US DOE under Contract No. DE-AC02-06CH11357."

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Acknowledgements

Synthesis, basic characterization experiments and all of the theoretical work were supported by the US Department of Energy, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences under award DE-FG02-12ER16362. Reactivity studies were supported by the Laboratory Directed Research and Development Program of Lawrence Berkeley National Laboratory under US Department of Energy Contract No. DE-AC02-05CH11231. Work at the Molecular Foundry, and XAS experiments performed at the Advanced Light Source (BL 10.3.2), Berkeley, were supported by the Office of Science, Office of Basic Energy Sciences, of the US Department of Energy under Contract No. DE-AC02-05CH11231. X-ray diffraction experiments were performed at the Advanced Photon Source at Argonne National Laboratory (17-BM-B). Use of the Advanced Photon Source, an Office of Science User Facility operated for the US Department of Energy (DOE) Office of Science by Argonne National Laboratory, was supported by the US DOE under Contract No. DE-AC02-06CH11357. S.B., F.B. and V.C. acknowledge financial support from the Ateneo Project 2011 ORTO11RRT5. We also thank the National Science Foundation for providing graduate fellowship support (D.J.X. and J.A.M.). In addition, we are grateful for the support of E.D.B. through a Gerald K. Branch fellowship in chemistry, P.V. through a Phillips 66 Excellence Fellowship and M.R.H. through the National Institute of Standards and Technology/National Research Council Fellowship Program. We thank S. Chavan for help with the infrared spectroscopy experiments and fruitful discussion.

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Contributions

D.J.X., E.D.B. and J.R.L. planned and executed the synthesis, characterization and reactivity studies. J.A.M., W.L.Q., M.R.H. and C.M.B. analysed the powder neutron and X-ray diffraction data. N.P. and P.V. performed the cluster DFT calculations. J.B. and K.L. performed the periodic DFT calculations. A.L.D. performed the CASSCF/PT2 calculations. D.G.T. and L.G. conceived and managed the computational efforts. F.B., V.C. and S.B. carried out the in situ transmission Fourier transform infrared studies, and J.Y. supervised EXAFS analysis. All authors participated in the preparation of the manuscript.

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Correspondence to Jeffrey R. Long.

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Supplementary information

Supplementary information

Supplementary information (PDF 4068 kb)

Supplementary information

Crystallographic data for compound 1+0.35 eq. N2O (CIF 209 kb)

Supplementary information

Crystallographic data for compound 1+0.6 eq. N2O (CIF 208 kb)

Supplementary information

Crystallographic data for compound 1+1.25 eq. N2O (CIF 209 kb)

Supplementary information

Crystallographic data for compound 2 at 100 K (CIF 317 kb)

Supplementary information

Crystallographic data for compound 2 at 298 K (CIF 321 kb)

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Xiao, D., Bloch, E., Mason, J. et al. Oxidation of ethane to ethanol by N2O in a metal–organic framework with coordinatively unsaturated iron(II) sites. Nature Chem 6, 590–595 (2014). https://doi.org/10.1038/nchem.1956

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