CaRLa-Catalysis Research Laboratory, Im Neuenheimer Feld 584, 69120 Heidelberg, Germany.
Chemistry. 2013 Aug 26;19(35):11661-71. doi: 10.1002/chem.201203893. Epub 2013 Jul 12.
In the search for a highly active and selective heterogenized metathesis catalyst, we systematically varied the pore geometry and size of various silica-based mesoporous (i.e., MCM-41, MCM-48, and SBA-15) and microporous (ZSM-5 and MWW) versus macroporous materials (D11-10 and Aerosil 200), besides other process parameters (temperature, dilution, and mean residence time). The activity and, especially, selectivity of such "linker-free" supports for ruthenium metathesis catalysts were evaluated in the cyclodimerization of cis-cyclooctene to form 1,9-cyclohexadecadiene, a valuable intermediate in the flavor and fragrance industry. The optimized material showed not only exceptionally high selectivity to the valuable product, but also turned out to be a truly heterogeneous catalyst with superior activity relative to the unsupported homogeneous complex.
在寻找高活性和选择性的异相复分解催化剂的过程中，我们系统地改变了各种基于硅的中孔（即 MCM-41、MCM-48 和 SBA-15）和微孔（ZSM-5 和 MWW）与大孔材料（D11-10 和 Aerosil 200）的孔几何形状和大小，以及其他工艺参数（温度、稀释度和平均停留时间）。我们评估了这些“无连接剂”的载体对钌复分解催化剂的活性，特别是选择性，在顺式环辛烯的环二聚反应中形成 1,9-环十六二烯，这是香精和香料工业中的一种有价值的中间体。优化后的材料不仅对有价值的产物表现出异常高的选择性，而且相对于无载体的均相配合物，它还是一种真正的多相催化剂，具有更高的活性。
