多齿配位体有机硅过渡金属络合催化剂——Ⅱ.聚-ω-(乙二胺基)十一烷基硅氧烷钯络合物的合成及其催化活性

THE SYNTHESIS AND ACTIVITY OF POLY-ω-(AMINOETHYLAMINO) UNDECYLSILO XANE PALLADIUM COMPLEX(Ⅱ)

本文报导聚-ω-(乙二胺基)十一烷基硅氧烷钯络合物的合成及其对不同底物的氢化,探讨钯催化剂对毒物的敏感性及不同溶剂的影响。实验结果表明:在无水乙醇溶剂中和一个氢压下,苯乙烯、丙烯腈、硝基苯均能在半小时左右完全氢化,而吡啶完全不能加氢。硫醚、硫醇对钯络合物有毒效,钯络合物对汞,空气不太敏感,而微量的醋酸汞,吡啶能使反应加速,各种溶剂对氢化活性的影响大致为:无水乙醇～四氢呋喃>二甲基甲酰胺>丙酮,钯络合物通过简单回收可再用。

The poly-ω-(aminoethylamino)undecylsiloxane palladium complex has been synthesized.The title complex displayed high activity for the hydrogenation of olefins and nitrobenzene in ethanol at 40℃ under an atmosphere pressure of hydrogen,Styrene.Acrylonitrile(0.004mool)and Nitrobenzene(0,0013)were completely hydrogenation with 50mg complex containing 3.78mg palladium wi- thin 0.5～0.68 hr.palladium complex is highly air stable.It stored under air for 0.83 year was nearly as active as freshly prepared one.The complex is sensitivity to thio-ether and thiol,but insensitivity to mercure.Rate of hy- drogenation can increase in the presence of 10μl pyridine and Hg(OAc)_2 The rate of hydrogenation decrease in a variety solvent in the order. Absolute alcohol～TH F>DMF>Ace tone The polymer complex can be easily recovered and reused.