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

Pengfei Ji†, Takahiro Sawano†, Zekai Lin, Ania Urban, Dean Boures, and Wenbin Lin* 

We report the stepwise, quantitative transformation of Ce^IV₆(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 Ce^III₆(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.