Department of Chemistry, University of Chicago , 929 East 57th Street, Chicago, Illinois 60637, United States.
J Am Chem Soc. 2017 May 24;139(20):7004-7011. doi: 10.1021/jacs.7b02394. Epub 2017 May 11.
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.
我们在这里报道了一种由三苯二甲酸（HTPDC）和一个前所未有的Zr 次级构筑单元（SBU）：Zr(μ-O)(μ-OH)(μ-OH)合成的坚固多孔的金属有机骨架（MOF），Zr-TPDC。Zr-SBU 可以看作是通过六个μ-OH 基团二聚化的两个常见的Zr 簇无机节点。Zr-TPDC SBU 与 CoCl 的金属化，然后用 NaBEtH 处理，得到了一种高活性和可重复使用的固体 Zr-TPDC-Co 催化剂，用于硝基芳烃、腈和异氰化物的加氢反应，得到相应的胺，具有优异的活性和选择性。这项工作突出了通过调节 SBU 的电子和空间性质来设计新型 MOF 负载的单原子固体催化剂的机会。
