为了证实过渡金属催化碳碳键交叉偶联反应的双金属效应,首次研究蒙脱土负载纳米钯铜双金属微粒催化Sonogahira交叉偶联反应.结合蒙脱土重金属吸附特性与DMF溶剂热羰化还原,发展了一种新的双金属纳米微粒合成方法,制备了钯铜比例为1∶1的双金属纳米微粒.催化条件优化实验发现,乙二醇二甲醚/水(V∶V=1∶4)混合体系为最佳溶剂.碳酸钾与三苯基膦存在下,MMT@Pd/Cu高效催化芳基碘与系列端炔的交叉偶联反应,以较好产率分离得到15个炔烃衍生物.动力学研究表明,水对蒙脱土片层的溶胀作用与Pd/Cu双金属协同效应是该催化剂高活性的关键.
To demonstrate the bimetallic effect of transition metal catalyzed C-C cross coupling, the montmorillonite (MMT) supported mixed palladium and copper nanoparticles were prepared and applied to catalytic Sonogashira couplings. A new method of preparing mixed metal nanoparticles was invented based on unique metal ion adsorption capacity of mont- morillonite and sequential reductive carbonylation via therrnolysis of N,N-dimethylformide, and POdCu bimetallic nanoparti- cals was prepared in the ratio of 1 ; 1. A mixed solvent system, dimethoxyethane/water (V : V= l : 4) was identified as the best solvent of the catalytic coupling. MMT@Pd/Cu catalyzed efficiently the cross-coupling of aryl iodides and terminal aryl- and alkyl-ynes in presence of potassium carbonate and triphenyl phosphine. 15 cross-coupling yne derivatives were isolated in excellent to moderate yields. Experimental kinetic study reveals that both swelling of montmorillonite promoted by water and Pd/Cu bimetallic synergistic effect play critical roles in high activity of the catalyst.