J. Phys. Chem. A 127,  5556-5564(2023)

What Determines If a Ligand Undergoes Coordination or Catalytic Activ-ation on a Metal Cluster

Wen Gan^1,2, Benben Huang^1,2, Klavs Hansen³, and Zhixun Luo^1,2,*

1 Beijing  National  Laboratory  for  Molecular Science,  State  Key  Laboratory  for Structural Chemistry of Unstable and Stable Species, Institute of Chemistry, Chinese Academy of Sciences, Beijing, 100190, China

2 University of Chinese Academy of Sciences, Beijing 100049, China

3 Center  for  Joint  QuantumStudies  and  Department  of  Physics,  School  of  Science, Tianjin University, 92 Weijin Road, Tianjin 300072, China

*zxluo@iccas.ac.cn

Abstract

We report a joint experimental and theoretical study on the reactivity of Ag_n⁺ clusters with H₂S, D₂O, and   NH₃. Complete dehydrogenation products are observed for Ag_n⁺ reacting with H₂S, but no dehydrogenation products are found for D₂O or NH₃ under the same reaction condition. Theoretical calculations elucidate why Ag_n⁺ clusters show different reactivities with these inorganic hydrides. NH₃ shows strong coordination with Ag_n⁺, but the dehydrogenation reactions are unfavorable; in contrast, the fragile H–S bonds and stable Ag_nS⁺ products facilitate the hydrogen evolution of H₂S on Ag_n⁺. We fully analyzed the metal–ligand interactions of Ag_n⁺ clusters with three molecules and illustrated the reaction dynamics and charge-transfer interactions and altered the superatomic states during the formation of cluster sulfides. We expect this study to benefit the design of stable environmentally friendly desulfurization catalysts and also the understanding of the mechanism on ligand-protected metal clusters in wet chemistry.