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. Thus repeated cycling induces no loss of activity, making this a promising route for mild aryl-ether bond scission.
Stavila, Vitalie, Parthasarathi, Ramakrishnan, Davis, Ryan W., El Gabaly, Farid, Sale, Kenneth L., Simmons, Blake A., Singh, Seema, & Allendorf, Mark D. (2015). MOF-based catalysts for selective hydrogenolysis of carbon–oxygen ether bonds. ACS Catalysis, 6(1). https://doi.org/10.1021/acscatal.5b02061
Stavila, Vitalie, Parthasarathi, Ramakrishnan, Davis, Ryan W., et al., "MOF-based catalysts for selective hydrogenolysis of carbon–oxygen ether bonds," ACS Catalysis 6, no. 1 (2015), https://doi.org/10.1021/acscatal.5b02061
@article{osti_1236475,
author = {Stavila, Vitalie and Parthasarathi, Ramakrishnan and Davis, Ryan W. and El Gabaly, Farid and Sale, Kenneth L. and Simmons, Blake A. and Singh, Seema and Allendorf, Mark D.},
title = {MOF-based catalysts for selective hydrogenolysis of carbon–oxygen ether bonds},
annote = {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. Thus repeated cycling induces no loss of activity, making this a promising route for mild aryl-ether bond scission.},
doi = {10.1021/acscatal.5b02061},
url = {https://www.osti.gov/biblio/1236475},
journal = {ACS Catalysis},
issn = {ISSN 2155-5435},
number = {1},
volume = {6},
place = {United States},
publisher = {American Chemical Society},
year = {2015},
month = {11}}