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Catalytic chemoselective functionalization of methane in a metal−organic framework

Abstract

Methane constitutes the largest fraction of natural gas reserves and is a low-cost abundant starting material for the synthesis of value-added chemicals and fuel. Selective catalytic functionalization of methane remains a vital goal in the chemical sciences due to its low intrinsic reactivity. Borylation has recently emerged as a promising route for the catalytic functionalization of methane. A major challenge in this regard is selective borylation towards the monoborylated product that is more active than methane and can easily lead to over-functionalization. Herein, we report a highly selective microporous metal−organic-framework-supported iridium(iii) catalyst for methane borylation that exhibits a chemoselectivity of >99% (mono versus bis at 19.5% yield; turnover number = 67) for monoborylated methane, with bis(pinacolborane) as the borylation reagent in dodecane, at 150 °C and 34 atm of methane. The preference for the monoborylated product is ascribed to the shape-selective effect of the metal−organic framework pore structures.

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Fig. 1: Reaction scheme of methane borylation with B2pin2.
Fig. 2: Synthetic scheme of the catalyst.
Fig. 3: Characterization of the catalyst.
Fig. 4: X-ray absorption spectroscopy characterization of the catalyst.

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Acknowledgements

This work was supported as part of the Inorganometallic Catalyst Design Center, an Energy Frontier Research Center funded by the US Department of Energy, Office of Science, Basic Energy Sciences, under award DESC0012702. Use of the Advanced Photon Source at the Argonne National Laboratory is supported by the US Department of Energy, Office of Science, Basic Energy Sciences, under contract DE-AC-02-06CH11357. MRCAT operations are supported by the Department of Energy and the MRCAT member institutions. This work made use of the IMSERC, Jerome B. Cohen X-Ray Diffraction, EPIC and KECK II facilities of Northwestern University’s NUANCE Center, which has received support from the Soft and Hybrid Nanotechnology Experimental Resource (NSF ECCS-1542205), the MRSEC programme (NSF DMR-1121262) at the Materials Research Center, the International Institute for Nanotechnology, the Keck Foundation and the State of Illinois, through the International Institute for Nanotechnology.

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X.Z., M.D. and O.K.F. designed the experiments. X.Z. and Z.H. carried out the synthesis of the materials with help from P.L. and T.C.W. under the supervision of M.D. and O.K.F. M.F. and Z.H. performed the high-throughput catalysis under the supervision of M.D. and O.K.F. X.Z., Z.H. and D.Y. characterized the materials and analysed the data with help from L.R. under the supervision of M.D. and O.K.F. X.Z., Z.H., L.R., M.D. and O.K.F. wrote the manuscript with contributions from all authors.

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Correspondence to Massimiliano Delferro or Omar K. Farha.

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Supplementary Methods; Supplementary Figures 1–12; Supplementary Table 1; Supplementary References

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Zhang, X., Huang, Z., Ferrandon, M. et al. Catalytic chemoselective functionalization of methane in a metal−organic framework. Nat Catal 1, 356–362 (2018). https://doi.org/10.1038/s41929-018-0069-6

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