Premium
The Synthesis, Bonding, and Transformation of a Ligand‐Protected Gold Nanohydride Cluster
Author(s) -
Dong Jia,
Gao ZeHua,
Zhang QianFan,
Wang LaiSheng
Publication year - 2021
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.202011748
Subject(s) - superatom , delocalized electron , chemistry , crystallography , cluster (spacecraft) , hydride , ligand (biochemistry) , catalysis , stereochemistry , metal , computational chemistry , electronic structure , organic chemistry , biochemistry , receptor , computer science , programming language
Gold does not react with H 2 to form bulk hydrides. Here we report the synthesis and characterization of a gold nanohydride protected by diphosphine ligands, [Au 22 H 4 (dppo) 6 ] 2+ [dppo=1,8‐bis(diphenylphosphino)octane]. The Au 22 core consists of two Au 11 units bonded by eight Au atoms not coordinated by the diphosphine ligands. The four H atoms are found to bridge the eight uncoordinated Au atoms at the interface. Each Au 11 unit can be viewed as a tetravalent superatom forming four delocalized Au‐H‐Au bonds, similar to the quadruple bond first discovered in the [Re 2 Cl 8 ] 2− inorganic cluster. The [Au 22 H 4 (dppo) 6 ] 2+ nanohydride is found to lose H atoms over an extended time via H evolution (H 2 ), proton (H + ) and hydride (H − ) releases. This complete repertoire of H‐related transformations suggests that the [Au 22 H 4 (dppo) 6 ] 2+ nanohydride is a versatile model catalyst for understanding the mechanisms of chemical reactions involving hydrogen on the surface of gold nanoparticles.