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Single-Site Cobalt Catalysts at New Zr123‑O)83‑OH)82‑OH)6 Metal–Organic Framework Nodes for Highly Active Hydrogenation of Nitroarenes, Nitriles, and Isocyanides

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posted on 06.05.2017, 00:00 by Pengfei Ji, Kuntal Manna, Zekai Lin, Xuanyu Feng, Ania Urban, Yang Song, Wenbin Lin
We report here the synthesis of a robust and porous metal–organic framework (MOF), Zr12-TPDC, constructed from triphenyl­dicarboxylic acid (H2TPDC) and an unprecedented Zr12 secondary building unit (SBU): Zr123-O)8­(μ3-OH)8­(μ2-OH)6. The Zr12-SBU can be viewed as an inorganic node dimerized from two commonly observed Zr6 clusters via six μ2-OH groups. The metalation of Zr12-TPDC SBUs with CoCl2 followed by treatment with NaBEt3H afforded a highly active and reusable solid Zr12-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.