Single-Site Cobalt Catalysts at New Zr(μ-O)(μ-OH)(μ-OH) Metal-Organic Framework Nodes for Highly Active Hydrogenation of Nitroarenes, Nitriles, and Isocyanides.

We report here the synthesis of a robust and porous metal-organic framework (MOF), Zr-TPDC, constructed from triphenyldicarboxylic acid (HTPDC) and an unprecedented Zr secondary building unit (SBU): Zr(μ-O)(μ-OH)(μ-OH). The Zr-SBU can be viewed as an inorganic node dimerized from two commonly observed Zr clusters via six μ-OH groups. The metalation of Zr-TPDC SBUs with CoCl followed by treatment with NaBEtH afforded a highly active and reusable solid Zr-TPDC-Co catalyst for the hydrogenation of nitroarenes, nitriles, and isocyanides to corresponding amines with excellent activity and selectivity. This work highlights the opportunity in designing novel MOF-supported single-site solid catalysts by tuning the electronic and steric properties of the SBUs.