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Bimetallic ZrZr-Hydride Complexes in Zirconocene Catalyzed Alkene Dimerization

机译:锆茂催化的烯烃二聚反应中的双金属ZrZr-氢化物配合物

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摘要

Being valuable precursors in the production of adhesives, lubricants, and other high-performance synthetic compounds, alkene dimers and oligomers can be obtained using homogeneous zirconocene catalytic systems. Further advances in such systems require precise control of their activity and chemoselectivity, increasing both the purity and yield of the products. This relies on the process mechanism usually built around the consideration of the hydride complexes as active intermediates in the alkene di- and oligomerization; however, the majority of studies lack the direct evidence of their involvement. Parallel studies on a well-known Cp ZrCl -AlR or HAlBu and a novel [Cp ZrH ] -ClAlR (R = Me, Et, Bu ) systems activated by methylaluminoxane (MMAO-12) have shown a deep similarity both in the catalytic performance and intermediate composition. As a result of the NMR studies, among all the intermediates considered, we proved that new Zr,Zr- hydride complexes having the type x[Cp ZrH ∙Cp ZrHCl∙ClAlR ]∙yMAO appear to be specifically responsible for the alkene dimerization with high yield.
机译:作为粘合剂,润滑剂和其他高性能合成化合物生产中的宝贵前体,可以使用均相的锆茂催化体系获得烯烃二聚体和低聚物。这种系统的进一步发展要求精确控制其活性和化学选择性,从而增加产物的纯度和产率。这依赖于通常围绕氢化物配合物作为烯烃二聚和低聚反应中的活性中间体的工艺机制。但是,大多数研究都缺乏直接参与的证据。对著名的Cp ZrCl -AlR或HAlBu以及由甲基铝氧烷(MMAO-12)活化的新型[Cp ZrH] -ClAlR(R = Me,Et,Bu)系统的并行研究表明,两者在催化性能上都具有相似性和中间成分。 NMR研究的结果表明,在所考虑的所有中间体中,我们证明了具有x [Cp ZrH∙Cp ZrHCl∙ClAlR]∙yMAO类型的新型Zr,Zr-氢化物络合物似乎是导致烯烃高二聚化的具体原因。让。

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