Bimetallic Zr,Zr-Hydride Complexes in Zirconocene Catalyzed Alkene Dimerization

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(2)ZrCl(2)-AlR(3) or HAlBu(i)(2) and a novel [Cp(2)ZrH(2)](2)-ClAlR(2) (R = Me, Et, Bu(i)) 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(2)ZrH(2)∙Cp(2)ZrHCl∙ClAlR(2)]∙yMAO appear to be specifically responsible for the alkene dimerization with high yield.