Palladium clusters size effects

Other suitable reaction solvents are aqueous tetrahydrofiiran, 1,2-diraethoxyethane or acetonitrile [28]. The same result was obtained by the method G, whereas 4-nitro-chlorobenzene was also coupled, in almost quantitative yield, within 2 h at 100 °C, or 87 h at room temperature. However, in the presence of tetra-n-butylammonium bromide (5 mol%), a soluble source of bromide anions, the SM reactions of aryl bromides have been effected in ethanol at room temperature in the presence of palladium(II) acetate or chloride (2 mol%) and potassium phosphate (2 eq.) as the base, even under exposure to air [55]. Palladium salts are reduced in situ with arylboronic acids to form catalytically active nano-sized palladium clusters (2-5 nm). The latter are stabilized by adsorbtion of one-layer bromide ions at the surface of each palladium-particle. Otherwise, the unstable nano-sized palladium-clusters are aggregated to the micro-sized catalytically inactive palladium black. In this manner, 2-bromonaphthalene (268) was reacted with 2-methoxyphenylboronic acid (269) to fiimish the biaryl 270 in 98% yield [55], respectively. Scheme 17. 

Other metallic clusters that have been demonstrated to show the QDL effect are palladium [116, 117], silver [118] and copper [119]. Palladium MFCs capped with mixed monolayers of hexanethiolate/dodecanethiolate and ferrocene thiolate ligands are prepared in a manner similar to that employed for gold MFCs. The DPV studies exhibit a quantized charging effect but the current peaks are not as well defined as those observed for Au-MPCs. Capacitance values of the order of 0.35 aF are obtained, indicating smaller core sizes or thicker monolayer dielectrics [116]. 

In a similar vein, Sakai, Takenaka and Torikai produced Nafion/metal microcomposites by reducing palladium, rhodium, platinum and silver ion-exchanged membranes with H, at high temperatures (100-300°C) (26). The affected metal clusters, distributed homogeneously, were about 50 A in size. As in Risen s work, a polymer matrix template effect appears to be operative. These systems were considered and evaluated within the context of gas separations technology. 

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