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 chemoselec...
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| Format: | Article |
| Language: | English |
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MDPI AG
2020-05-01
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| Series: | Molecules |
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| Online Access: | https://www.mdpi.com/1420-3049/25/9/2216 |
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| author | Lyudmila V. Parfenova Pavel V. Kovyazin Almira Kh. Bikmeeva |
| author_facet | Lyudmila V. Parfenova Pavel V. Kovyazin Almira Kh. Bikmeeva |
| author_sort | Lyudmila V. Parfenova |
| collection | DOAJ |
| description | 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<sub>2</sub>ZrCl<sub>2</sub>-AlR<sub>3</sub> or HAlBu<sup>i</sup><sub>2</sub> and a novel [Cp<sub>2</sub>ZrH<sub>2</sub>]<sub>2</sub>-ClAlR<sub>2</sub> (R = Me, Et, Bu<sup>i</sup>) 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<sub>2</sub>ZrH<sub>2</sub>∙Cp<sub>2</sub>ZrHCl∙ClAlR<sub>2</sub>]∙yMAO appear to be specifically responsible for the alkene dimerization with high yield. |
| first_indexed | 2024-03-10T19:57:57Z |
| format | Article |
| id | doaj.art-e8510cd5843b4f6faf0d901fae2defe1 |
| institution | Directory Open Access Journal |
| issn | 1420-3049 |
| language | English |
| last_indexed | 2024-03-10T19:57:57Z |
| publishDate | 2020-05-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Molecules |
| spelling | doaj.art-e8510cd5843b4f6faf0d901fae2defe12023-11-19T23:51:51ZengMDPI AGMolecules1420-30492020-05-01259221610.3390/molecules25092216Bimetallic Zr,Zr-Hydride Complexes in Zirconocene Catalyzed Alkene DimerizationLyudmila V. Parfenova0Pavel V. Kovyazin1Almira Kh. Bikmeeva2Institute of Petrochemistry and Catalysis of Russian Academy of Sciences, 141, Prospekt Oktyabrya, 450075 Ufa, RussiaInstitute of Petrochemistry and Catalysis of Russian Academy of Sciences, 141, Prospekt Oktyabrya, 450075 Ufa, RussiaInstitute of Petrochemistry and Catalysis of Russian Academy of Sciences, 141, Prospekt Oktyabrya, 450075 Ufa, RussiaBeing 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<sub>2</sub>ZrCl<sub>2</sub>-AlR<sub>3</sub> or HAlBu<sup>i</sup><sub>2</sub> and a novel [Cp<sub>2</sub>ZrH<sub>2</sub>]<sub>2</sub>-ClAlR<sub>2</sub> (R = Me, Et, Bu<sup>i</sup>) 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<sub>2</sub>ZrH<sub>2</sub>∙Cp<sub>2</sub>ZrHCl∙ClAlR<sub>2</sub>]∙yMAO appear to be specifically responsible for the alkene dimerization with high yield.https://www.mdpi.com/1420-3049/25/9/2216zirconocenemetal hydridesmethylaluminoxanealkene dimerizationnuclear magnetic resonance |
| spellingShingle | Lyudmila V. Parfenova Pavel V. Kovyazin Almira Kh. Bikmeeva Bimetallic Zr,Zr-Hydride Complexes in Zirconocene Catalyzed Alkene Dimerization Molecules zirconocene metal hydrides methylaluminoxane alkene dimerization nuclear magnetic resonance |
| title | Bimetallic Zr,Zr-Hydride Complexes in Zirconocene Catalyzed Alkene Dimerization |
| title_full | Bimetallic Zr,Zr-Hydride Complexes in Zirconocene Catalyzed Alkene Dimerization |
| title_fullStr | Bimetallic Zr,Zr-Hydride Complexes in Zirconocene Catalyzed Alkene Dimerization |
| title_full_unstemmed | Bimetallic Zr,Zr-Hydride Complexes in Zirconocene Catalyzed Alkene Dimerization |
| title_short | Bimetallic Zr,Zr-Hydride Complexes in Zirconocene Catalyzed Alkene Dimerization |
| title_sort | bimetallic zr zr hydride complexes in zirconocene catalyzed alkene dimerization |
| topic | zirconocene metal hydrides methylaluminoxane alkene dimerization nuclear magnetic resonance |
| url | https://www.mdpi.com/1420-3049/25/9/2216 |
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