Mechanistic Study of the Hydride Migration-Induced Reversible Isomerization in Au22(SR)15H Isomers

• Published in: Journal of the American Chemical Society Vol. 145; no. 29; pp. 15859 - 15868
• Main Authors: Li, Qinzhen, Tan, Yesen, Huang, Baoyu, Yang, Sha, Chai, Jinsong, Wang, Xiaoping, Pei, Yong, Zhu, Manzhou
• Format: Journal Article
• Language: English
• Published: American Chemical Society 26.07.2023
• ISSN: 0002-7863; 1520-5126
• DOI: 10.1021/jacs.3c02768

Unraveling the evolution mechanism of metal nanoclusters is of great importance in understanding the formation and evolution of metallic condensed matters. In this work, the specific evolution process between a pair of gold nanocluster (Au NC) isomers is completely revealed by introducing hydride ligands to simplify the research system. A hydride-containing Au NC, Au22(SR)15H, was synthesized by kinetic control, and the positions of the hydrides were then confirmed by combining X-ray diffraction, neutron diffraction, and DFT calculations. Importantly, a reversible structural isomerization was found to occur on this Au22(SR)15H. By combining the crystal structures and theoretical calculations, the focus was placed on the hydride-binding site, and a [Au–H] migration mechanism of this isomerization process is clearly shown. Furthermore, this [Au–H] migration mechanism is confirmed by the subsequent capture and structural determination of theoretically predicted intermediates. This work provides insight into the dynamic behavior of hydride ligands in nanoclusters and a strategy to study the evolution mechanism of nanoclusters by taking the hydride ligand as the breakthrough point.