Yang Song†, Zhe Li†, Pengfei Ji, Michael Kaufmann, Xuanyu Feng, Justin S. Chen, Cheng Wang, and Wenbin Lin*
Herein we report that the Ti8-BDC (MIL-125) (BDC is 1,4-benzenecarboxylate) metal–organic framework (MOF) supports single-site solid NiII-hydride catalyst for the hydrogenolysis of aryl ethers containing α-O-4, β-O-4, and 4-O-5 linkages to exclusively afford hydrocarbons under mild conditions without the addition of a base. The catalytic activity of Ti8-BDC-NiH is highly dependent on the reduction of Ti8(μ2-O)8(μ2-OH)4 nodes. Density functional theory (DFT) calculations revealed two key steps of σ-bond metathesis in the catalytic cycle of Ti8-BDC-NiH catalyzed hydrogenolysis. This work highlights the potential of MOF-supported single-site catalysts in aryl ether bond scission and other processes for the efficient production of biofuels and chemical feedstocks.