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 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.