A Homoleptic Alkynyl-Ligated [Au13 Ag16 L24 ]3- Cluster as a Catalytically Active Eight-Electron Superatom.

A new alkynylated cluster [Au13 Ag16 (C10 H6 NO)24 ]3- is prepared by a NaBH4 mediated reduction method. The AuAg clusters are confirmed by sophisticated characterization techniques. It has a unique "Aucenter @Ag12 @Au12 Ag4 " metal framework which is protected by 24 atypical alkyne ligands L (L=C10 H6 NO). The ligands construct a unique type of motif L-(Ag)-Au-(Ag)-L at the cluster interface, where the alkyne (C≡C) group of each L was linked by sharing an Au atom through the σ bonds and each C≡C group was discretely connected to a chemically different Ag atom (Agicosahedral /Agcap ) through π bonds. The electronic and optical properties of [Au13 Ag16 L24 ]3- were studied. DFT characterized the cluster as a clear 8-electron superatom, and peaks in the optical absorption spectrum were interpreted in terms of the P and D superatom states. The supported Au13 Ag16 L24 /CeO2 catalyst exhibited high catalytic activity and selectivity towards the A3 -coupling reaction involving benzaldehyde, diethylamine, and phenylacetylene.