Alternative synthetic route for the heterometallic CO-releasing [Sb@Rh12(CO)27]3− icosahedral carbonyl cluster and synthesis of its new unsaturated [Sb@Rh12(CO)24]4− and dimeric [{Sb@Rh12Sb(CO)25}2Rh(CO)2PPh3]7− derivatives

The evolution of the optical absorption spectrum of bimetallic Ag-Au monolayer-protected clusters (MPC) obtained by progressively doping Ag into the experimentally known structure of Au133(SR)52 was predicted via rigorous time-dependent density-functional theory (TDDFT) calculations. In addition to monometallic Au133(SR)52 and Ag133(SR)52 species, 5 different (Ag-Au)133(SR)52 homotops were considered with varying Ag content and site positioning, and their electronic structure and optical response were analyzed in terms of Projected Density Of States (PDOS), the induced or transition electron density, and Transition Component Maps (TCM) at selected excitation energies. It was found that Ag doping led to the effects rather different from those encountered in bare metal clusters. And it was also observed that Ag doping could produce structured spectral features, especially in the 3–4 eV range but also in the optical region if Ag atoms were located in the sub-staple region, as rationalized by the accompanying electronic analysis. Additionally, Au doping into the staples of Ag-rich MPC also gave rise to a more homogeneous induced electron density. These findings show the great sensitivity of the electronic response of MPC nanoalloy systems to the exact location of the alloying sites.     

Effects of doping in 25-atom bimetallic nanocluster catalysts for carbon–carbon coupling reaction of iodoanisole and phenylacetylene

We here report the catalytic effects of foreign atoms (Cu, Ag, and Pt) doped into well-defined 25-gold-atom nanoclusters. Using the carbon-carbon coupling reaction of p-iodoanisole and phenylacetylene as a model reaction, the gold-based bimetallic MxAu25?x(SR)18 (–SR=–SCH2CH2Ph) nanoclusters (supported on titania) were found to exhibit distinct effects on the conversion of p-iodoanisole as well as the selectivity for the Sonogashira cross-coupling product, 1-methoxy-4-(2-phenylethynyl)benzene). Compared to Au25(SR)18, the centrally doped Pt1Au24(SR)18 causes a drop in catalytic activity but with the selectivity retained, while the AgxAu25?x(SR)18 nanoclusters gave an overall performance comparable to Au25(SR)18. Interestingly, CuxAu25?x(SR)18 nanoclusters prefer the Ullmann homo-coupling pathway and give rise to product 4,4′-dimethoxy-1,1′-biphenyl, which is in opposite to the other three nanocluster catalysts. Our overall conclusion is that the conversion of p-iodoanisole is largely affected by the electronic effect in the bimetallic nanoclusters’ 13-atom core (i.e., Pt1Au12, CuxAu13?x, and Au13, with the exception of Ag doping), and that the selectivity is primarily determined by the type of atoms on the MxAu12?x shell (M=Ag, Cu, and Au) in the nanocluster catalysts.