Shen Hui, Wu Qingyuan, Malola Sami, Han Ying-Zi, Xu Zhen, Qin Ruixuan, Tang Xiongkai, Chen Yang-Bo, Teo Boon K, Häkkinen Hannu, Zheng Nanfeng
State Key Laboratory for Physical Chemistry of Solid Surfaces, Collaborative Innovation Center of Chemistry for Energy Materials, and National & Local Joint Engineering Research Center for Preparation Technology of Nanomaterials, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, China.
Departments of Physics and Chemistry, Nanoscience Center, University of Jyväskylä, Jyväskylä FI-40014, Finland.
J Am Chem Soc. 2022 Jun 22;144(24):10844-10853. doi: 10.1021/jacs.2c02669. Epub 2022 Jun 7.
The complexity of heterogeneous metal catalysts makes it challenging to gain insights into their catalytic mechanisms. Thus, there exists a huge gap between heterogeneous catalysis and organometallic catalysis. With the success in the preparation of highly robust atomically precise metal nanocluster catalysts (i.e., [Au(NHC-1)(PA)Br] and [Au(NHC-1)(PA)Br], where NHC-1 is a bidentate NHC ligand, and PA is phenylacetylide) with surface organometallic motifs anchored on the metallic core, we demonstrate in this work how the metallic core works synergistically with the surface organometallic motifs to enhance the catalysis. More importantly, the discovery allows the development of highly stable and recyclable heterogeneous metal catalysts to achieve efficient hydroamination of alkynes with an extremely low catalyst dosage (0.002 mol %), helping bridge the gap between heterogeneous and homogeneous metal catalysis. The surface modification of metal nanocatalysts with organometallic motifs provides a new design principle of metal catalysts with enhanced catalysis.
多相金属催化剂的复杂性使得深入了解其催化机制具有挑战性。因此，多相催化与有机金属催化之间存在巨大差距。随着成功制备出具有锚定在金属核上的表面有机金属基序的高度稳健的原子精确金属纳米簇催化剂（即[Au(NHC - 1)(PA)Br]和[Au(NHC - 1)(PA)Br]，其中NHC - 1是双齿NHC配体，PA是苯乙炔基），我们在这项工作中展示了金属核如何与表面有机金属基序协同作用以增强催化作用。更重要的是，这一发现使得能够开发出高度稳定且可循环使用的多相金属催化剂，以极低的催化剂用量（0.002 mol%）实现炔烃的高效氢胺化反应，有助于弥合多相和均相金属催化之间的差距。用有机金属基序对金属纳米催化剂进行表面修饰为具有增强催化作用的金属催化剂提供了一种新的设计原则。
