Cerium-Hydride Secondary Building Units in a Porous Metal–Organic Framework for Catalytic Hydroboration and Hydrophosphination

We report the stepwise, quantitative transformation of Ce IV 6 (μ 3 -O) 4 (μ 3 -OH) 4 (OH) 6 (OH 2 ) 6 nodes in a new Ce-BTC (BTC = trimesic acid) metal–organic framework (MOF) into the first Ce III 6 (μ 3 -O) 4 (μ 3 -OLi) 4 (H) 6 (THF) 6 Li 6 metal-hydride nodes that effectively catalyze hydroboration and hydrophosphination reactions. CeH-BTC displays low steric hindrance and electron density compared to homogeneous organolanthanide catalysts, which likely accounts for the unique 1,4-regioselectivity for the hydroboration of pyridine derivatives. MOF nodes can thus be directly transformed into novel single-site solid catalysts without homogeneous counterparts for sustainable chemical synthesis.