Catalytic asymmetric allylation of aldehydes with allylic trimethoxysilanes was achieved with the p-Tol-BINAP small middle dotAgF complex as catalyst [Eq. (a); p-Tol-BINAP=2,2'-bis(di-p-tolylphosphanyl)-1,1'-binaphthyl)]. High anti and enantioselectivities were obtained in the reaction with crotyltrimethoxysilane, irrespective of the configuration at the double bond.

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The hydrogen permeability of Pd-Ag alloy membranes has been investigated over a wide temperature range between 100 C and 500 C. The hydrogen permeation coef cient, Φ, for Pd-23mol%Ag decreases with decreasing temperature above 300 C, in good agreement with the previous literature. However, Φ starts to increases below 250 C, and a peak is observed at around 180 C. Considering the silver concentration and operating temperature, the α-α phase transition never occurs in this condition. In other words, the α-α phase transition is not the reason for the anomalous peak behavior of Pd-23mol%Ag alloy at low temperature. In addition, it is con rmed that the diffusion-limiting hydrogen permeation reaction takes place from room temperature up to 500 C. To understand the reason for the peak appearance, the hydrogen permeability has been analyzed in view of the new description of hydrogen permeation based on hydrogen chemical potential. As a result, it is found that the temperature dependence of the PCT factor, f PCT , is dominant for the peak appearance, meaning that the corresponding pressure-composition-isotherms (PCT curves) are essential for the understanding of hydrogen permeability of the alloy. Dependences of the pressure condition and silver concentration on the peak behavior have also been investigated. The peak temperature increases with increasing the hydrogen pressure at feed side. In addition, the peak appears at lower temperature and becomes remarkable with decreasing silver concentration of Pd-Ag alloy membrane. In other words, the composition of Pd-Ag alloy membranes must be designed based on the operating temperature or pressure condition. Thus, this study suggests new possibilities of alloy design for Pd-Ag alloy membranes.

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