RESUMO
This paper describes the unique catalytic activity of bimetallic Au/Pd alloy nanoclusters (NCs) for Ullmann coupling of chloroarenes in aqueous media at low temperature. The corresponding reaction cannot be achieved by monometallic Au and Pd NCs as well as their physical mixtures. On the basis of quantum chemical calculation, it was found that the crucial step to govern the unusual catalytic activity of Au/Pd is the dissociative chemisorption of ArCl, which is unlikely in the monometallic Au and Pd NCs.
RESUMO
The photoluminescence properties of aryl iodides chemisorbed on gold nanoparticles were examined. Chemisorption of a series of aryl iodides onto poly(N-vinylpyrrolidone)-protected Au nanoparticles (Au:PVP) in solution resulted in highly enhanced luminescence. Kinetic studies revealed that the photoluminescence is derived from the excimer formation of aryl iodides on Au:PVP, and the process is significantly faster than intersystem crossing by the heavy atom.
RESUMO
New catalytic activity of gold/palladium alloy nanoclusters (NCs) for carbon-halogen bond activation is demonstrated. In the case of an aryl chloride, the inclusion of gold in a bimetallic catalyst is indispensable to achieve the coupling reactions. Gold has the unique effect of stabilizing palladium, such that Pd(2+) leached from clusters by means of spillover of chloride during oxidative addition. The thus-formed spillover intermediate further reacts heterogeneously in both Ullmann and Suzuki-type coupling reactions through a new type of mechanism. In the case of an aryl bromide, Ullmann coupling occurs through the spillover of bromide, similar to that of aryl chloride. However, a significant fraction of palladium also leached, which diminished the Ullmann coupling activity of the aryl bromide and, as a result, the order of reactivity was ArCl>ArBr. With regard to the activation of the C-Br bond towards a Suzuki-type reaction, the inclusion of a higher gold content in gold/palladium clusters stabilized palladium to prevent the leaching of Pd(2+) from the clusters by means of spillover of bromide. The spillover intermediate reacts heterogeneously with PhB(OH)2, palladium-rich gold/palladium, or pure palladium clusters; the oxidative addition of ArBr favors the extraction of palladium from the clusters, yielding Pd(2+) intermediates. The extracted intermediates react homogenously (Pd(2+/)Pd(0) catalysis) with PhB(OH)2, which results in the higher selectivity of the cross-coupling product. An initial step to observe such unprecedented halide dependency, together with the dynamic behavior of palladium on the surface of gold is the oxidative addition of Ar-X. A detailed insight into the first oxidative addition process was also examined by quantum chemical calculations.
RESUMO
The strong inhibitor effect of aryl iodides on the quasi-homogenous gold-catalyzed oxidation reaction was described. Aryl iodides were adsorbed on the exposed surface of Au clusters, which affected the accessibility of the nanoclusters to the reacting species and acted as strong inhibitors in catalysis.