MOF-Based Catalysts for Selective Hydrogenolysis of Carbon–Oxygen Ether Bonds

MOF-Based Catalysts for Selective Hydrogenolysis of Carbon–Oxygen Ether Bonds

We demonstrate that metal–organic frameworks (MOFs) can catalyze hydrogenolysis of aryl ether bonds under mild conditions. Mg-IRMOF-74­(I) and Mg-IRMOF-74­(II) are stable under reducing conditions and can cleave phenyl ethers containing β-O-4, α-O-4, and 4-O-5 linkages to the corresponding hydrocarb...

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Veröffentlicht in:ACS catalysis 2016-01, Vol.6 (1), p.55-59
Hauptverfasser: Stavila, Vitalie, Parthasarathi, Ramakrishnan, Davis, Ryan W, El Gabaly, Farid, Sale, Kenneth L, Simmons, Blake A, Singh, Seema, Allendorf, Mark D
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container_end_page 59
container_issue 1
container_start_page 55
container_title ACS catalysis
container_volume 6
creator Stavila, Vitalie
Parthasarathi, Ramakrishnan
Davis, Ryan W
El Gabaly, Farid
Sale, Kenneth L
Simmons, Blake A
Singh, Seema
Allendorf, Mark D
description We demonstrate that metal–organic frameworks (MOFs) can catalyze hydrogenolysis of aryl ether bonds under mild conditions. Mg-IRMOF-74­(I) and Mg-IRMOF-74­(II) are stable under reducing conditions and can cleave phenyl ethers containing β-O-4, α-O-4, and 4-O-5 linkages to the corresponding hydrocarbons and phenols. Reaction occurs at 10 bar H2 and 120 °C without added base. DFT-optimized structures and charge transfer analysis suggest that the MOF orients the substrate near Mg2+ ions on the pore walls. Ti and Ni doping further increase conversions to as high as 82% with 96% selectivity for hydrogenolysis versus ring hydrogenation. Repeated cycling induces no loss of activity, making this a promising route for mild aryl-ether bond scission.
doi_str_mv 10.1021/acscatal.5b02061
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