J. Am. Chem. Soc. 2017, 139, 20, 7004–7011

Pengfei Ji†, Kuntal Manna†, Zekai Lin, Xuanyu Feng, Ania Urban, Yang Song, and 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): 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.