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- Title
Ligand Engineering toward the Trade‐Off between Stability and Activity in Cluster Catalysis.
- Authors
Guan, Zong‐Jie; He, Rui‐Lin; Yuan, Shang‐Fu; Li, Jiao‐Jiao; Hu, Feng; Liu, Chun‐Yu; Wang, Quan‐Ming
- Abstract
We report the structures, stability and catalysis properties of two Ag21 nanoclusters, namely [Ag21(H2BTCA)3(O2PPh2)6]SbF6 (1) and [Ag21(C≡CC6H3‐3,5‐R2)6(O2PPh2)10]SbF6 (2) (H4BTCA=p‐tert‐butylthiacalix[4]arene, R=OMe). Both Ag21 structures possess an identical icosahedral kernel that is surrounded by eight peripheral Ag atoms. Single‐crystal structural analysis and ESI‐MS revealed that 1 is an 8‐electron cluster and 2 has four free electrons. Theoretical results show that the P‐symmetry orbitals are found as HOMO‐1 and HOMO states in 1, and the frontier unoccupied molecular orbitals (LUMO, LUMO+1 and LUMO+2) show D‐character, indicating 1 is a superatomic cluster with an electronically closed shell 1S21P6, while 2 has an incomplete shell configuration 1S21P2. These two Ag21 clusters show superior stability under ambient conditions, and 1 is robust even at 90 °C in toluene and under oxidative conditions (30 % H2O2). Significantly, 2 exhibits much higher activity than 1 as catalyst in the reduction of 4‐nitrophenol. This work demonstrates that ligands can influence the electronic structures of silver clusters, and further affect their stability and catalytic performance.
- Subjects
CATALYTIC activity; SILVER clusters; CATALYSTS; ELECTRONIC structure; ATOMS; FRONTIER orbitals
- Publication
Angewandte Chemie, 2022, Vol 134, Issue 11, p1
- ISSN
0044-8249
- Publication type
Article
- DOI
10.1002/ange.202116965