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

We report the stepwise, quantitative transformation of CeIV6(μ3-O)4(μ3-OH)4(OH)6(OH2)6 nodes in a new Ce-BTC (BTC = trimesic acid) metal–organic framework (MOF) into the first CeIII6(μ3-O)4(μ3-OLi)4(H)6(THF)6Li6 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.