Highly Robust but Surface-Active: An N-Heterocyclic Carbene-Stabilized Au₂₅ Nanocluster

Surface organic ligands play a critical role in stabilizing atomically precise metal nanoclusters in solutions. However, it is still challenging to prepare highly robust ligated metal nanoclusters that are surface-active for liquid-phase catalysis without any pre-treatment. Now, an N-heterocyclic carbene-stabilized Au₂₅ nanocluster with high thermal and air stabilities is presented as a homogenous catalyst for cycloisomerization of alkynyl amines to indoles. The nanocluster, characterized as [Au₂₅ (ⁱ Pr₂ -bimy)₁₀ Br₇ ]²⁺ (ⁱ Pr₂ -bimy=1,3-diisopropylbenzimidazolin-2-ylidene) (1), was synthesized by direct reduction of AuSMe₂ Cl and ⁱ Pr₂ -bimyAuBr with NaBH₄ in one pot. X-ray crystallization analysis revealed that the cluster comprises two centered Au₁₃ icosahedra sharing a vertex. Cluster 1 is highly stable and can survive in solution at 80 °C for 12 h, which is superior to Au₂₅ nanoclusters passivated with phosphines or thiols. DFT computations reveal the origins of both electronic and thermal stability of 1 and point to the probable catalytic sites. This work provides new insights into the bonding capability of N-heterocyclic carbene to Au in a cluster, and offers an opportunity to probe the catalytic mechanism at the atomic level.