Journal of the American Chemical Society
Journal of the American Chemical Society
5 years ago

Single-Site Cobalt Catalysts at New Zr12(μ3-O)8(μ3-OH)8(μ2-OH)6 Metal–Organic Framework Nodes for Highly Active Hydrogenation of Nitroarenes, Nitriles, and Isocyanides

Single-Site Cobalt Catalysts at New Zr12(μ3-O)8(μ3-OH)8(μ2-OH)6 Metal–Organic Framework Nodes for Highly Active Hydrogenation of Nitroarenes, Nitriles, and Isocyanides
Zekai Lin, Ania Urban, Pengfei Ji, Kuntal Manna, Yang Song, Wenbin Lin, Xuanyu Feng
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): Zr12(μ3-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.

Publisher URL: http://dx.doi.org/10.1021/jacs.7b02394

DOI: 10.1021/jacs.7b02394

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