Monoarsine-protected icosahedral cluster [Au₁₃(AsPh₃)₈Cl₄]⁺: comparative studies on ligand effect and surface...

Ligand shells of gold nanoclusters play important roles in regulating their molecular and electronic structures. However, the similar but distinct impacts of the homologous analogues of the protecting ligands remain elusive. The C_2v symmetric monoarsine-protected cluster [Au₁₃(AsPh₃)₈Cl₄]⁺ (Au₁₃As₈) was facilely prepared by direct reduction of (Ph₃As)AuCl with NaBH₄. This cluster is isostructural with its previously reported stibine analogue [Au₁₃(SbPh₃)₈Cl₄]⁺ (Au₁₃Sb₈), enabling a comparative study between them. Au₁₃As₈ exhibits a blue-shifted electronic absorption band, and this is probably related to the stronger π-back donation interactions between the Au₁₃ core and AsPh₃ ligands, which destabilize its superatomic 1P and 1D orbitals. In comparison to the thermodynamically less stable Au₁₃Sb₈, Au₁₃As₈ achieves a better trade-off between catalytic stability and activity, as demonstrated by its excellent catalytic performance towards the aldehyde-alkyne-amine (A³) coupling reaction. Moreover, the ligand exchange reactions between Au₁₃As₈ with phosphines, as exemplified by PPh₃ and Ph₂P(CH₂)₂PPh₂, suggest that Au₁₃As₈ may be a good precursor cluster for further cluster preparation through the "cluster-to-cluster" route.