无机高分子Ru-M双金属络合物在苯甲酸乙酯氢化生成环已基甲醇反应中的催化作用

Catalytic Behavior of Inorganic Polymer-Ru-M Dimetallic Complexes for the Hydrogenation of Ethyl Benzoate to Cyclohexylcarbinol

合成了SiO_2负载的聚铝氨烷(Al-N)、聚硅氨烷(Si-N)、聚钛氨烷(Ti-N)和聚锡氨烷(Sn-N)的钌-铬双金属络合物(M’-N-Ru-Cr,M’=Al、Si、Ti或Sn),考察了这些无机高分子-Ru-Cr双金属络合物对苯甲酸乙酯氢化反应生成环己基甲醇的催化作用,其催化活性顺序为:Al-N-Ru-Cr>Sn-N-Ru-Cr>Si-N-Ru-Cr>Ti-N-Ru-Cr.反应体系中加入适量的水可使Al-N-Ru-Cr的催化活性明显提高,改变Al-N-Ru-Cr的Ru/Cr比例或使用不同溶剂均对环己基甲醇的收率有显著的影响.用测定转化数的方法研究了Al-N-Ru-Cr的稳定性.

Ruthenium and chromium bimetallic complexes of silica-supported polyalumazane (Al-N), polysilazane(Si-N), polystannazane(Sn-N) and polytitanazane(Ti-N) were prepared. The catalytic behavior of these complexes(M'-N-Ru-Cr, M'=Al. Si, Ti or Sn)for the hydrogenation of ethyl benzoate to cyclohexylcarbinol has been investigated. The order of the catalytic activities of these catalysts is as follows: Al-N-Ru-Cr>Sn-N-Ru-Cr>Si-N-Ru-Cr>Ti-N-Ru-Cr.The catalytic activities can be increased markedly when proper amount of water was added to the reaction system. The ratio of Ru/ Cr and the nature of solvent also influenced the yield of cyclohexylcarbinol. The stability of Al-N-Ru-Cr catalyst was studied in terms of changes in the turnover number.