Highly Robust but Surface-Active : An N-Heterocyclic Carbene-Stabilized Au25 Nanocluster
Shen, H., Deng, G., Kaappa, S., Tan, T., Han, Y.-Z., Malola, S., Lin, S.-C., Teo, B. K., Häkkinen, H., & Zheng, N. (2019). Highly Robust but Surface-Active : An N-Heterocyclic Carbene-Stabilized Au25 Nanocluster. Angewandte Chemie, 58(49), 17731-17735. https://doi.org/10.1002/anie.201908983
Published inAngewandte Chemie
© 2019 Wiley‐VCH Verlag GmbH & Co. KGaA, Weinheim
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(iPr2-bimy)10Br7]2+ (iPr2-bimy=1,3-diisopropylbenzimidazolin-2-ylidene) (1), was synthesized by direct reduction of AuSMe2Cl and iPr2-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. ...
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Additional information about fundingWe thank the National Key R&D Program of China (2017YFA0207304), the NSF of China (21890752, 21731005, 21420102001, 21721001), and the fundamental research funds for central universities (20720190043) for financial support. The computational work in the University of Jyväskylä was supported by the Academy of Finland through H.H.’s Academy Professorship. H.H. acknowledges support from China's National Innovation and Intelligence Introduction Base visitor program. S.K. thanks the Väisälä Foundation for a personal PhD study grant. The computations were made at the CSC supercomputing center in Finland. ...
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