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


We report the stepwise, quantitative transformation of Ce<sup>IV</sup><sub>6</sub>(μ<sub>3</sub>-O)<sub>4</sub>(μ<sub>3</sub>-OH)<sub>4</sub>­(OH)<sub>6</sub>(OH<sub>2</sub>)<sub>6</sub> nodes in a new Ce-BTC (BTC = trimesic acid) metal–organic framework (MOF) into the first Ce<sup>III</sup><sub>6</sub>(μ<sub>3</sub>-O)<sub>4</sub>(μ<sub>3</sub>-OLi)<sub>4</sub>(H)<sub>6</sub>(THF)<sub>6</sub>Li<sub>6</sub> 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

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