State Key Laboratory for Oxo Synthesis and Selective Oxidation, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, No.18, Tianshui Middle Road, Lanzhou, P.R. China.
School of Environment and Civil Engineering, Dongguan University of Technology, No.1, Daxue Rd. Songshan Lake, Dongguan, Guangdong Province, P.R. China.
Chemistry. 2018 Nov 7;24(62):16588-16594. doi: 10.1002/chem.201803364. Epub 2018 Oct 17.
A series of porous organic polymers (POPs) based on N-heterocyclic carbene (NHC) building blocks has been prepared through an octacarbonyldicobalt complex [Co (CO) ]-catalyzed trimerization of terminal alkyne groups. By changing the monomer ratio in the copolymerization, cross-linked POPs with tunable surface areas of 485-731 m g and pore volumes of 0.31-0.51 cm g were easily prepared. Compared with the analogues homogeneous NHC (SIPr) catalysts, the POPs exhibited an enhanced catalytic activity and high selectivity in the reductive functionalization of CO with amines. The extraordinary performance of the sample could be attributed to the combination of the gas enrichment (or storage) effect, enhanced in-pore concentrations of other substrates, and advantageous micropore structures of the porous polymers. Meanwhile, these catalysts can easily be separated and recycled from the reaction systems with only a slight loss of activity. This excellent catalytic performance and facile recycling of heterogeneous catalysts make them very attractive. These NHC-containing POPs may provide a new platform for catalytic transformations of CO .
通过八羰基二钴[Co(CO) ]配合物催化的末端炔基三聚反应，制备了一系列基于 N-杂环卡宾（NHC）构筑块的多孔有机聚合物（POPs）。通过改变共聚单体比例，可轻松制备具有可调比表面积（485-731 m 2 g -1 ）和孔体积（0.31-0.51 cm 3 g -1 ）的交联 POPs。与类似的均相 NHC（SIPr）催化剂相比，POPs 在胺与 CO 的还原官能化反应中表现出更高的催化活性和选择性。该样品的优异性能可归因于气体富集（或存储）效应、增强的孔内其他底物浓度以及多孔聚合物有利的微孔结构的结合。同时，这些催化剂可以很容易地从反应体系中分离和回收，活性损失很小。这种优异的催化性能和易于回收的多相催化剂使它们非常有吸引力。这些含 NHC 的 POPs 可能为 CO 的催化转化提供新的平台。
