Experimental and Theoretical Study of Zirconocene-Catalyzed Oligomerization of 1-Octene
Zirconocene-catalyzed coordination oligomerization of higher α-olefins is of theoretical and practical interest. In this paper, we present the results of experimental and theoretical study of α-olefin oligomerization, catalyzed by (η<sup>5</sup>-C<sub>5</sub>H<sub>5<...
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MDPI AG
2020-07-01
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| Series: | Polymers |
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| Online Access: | https://www.mdpi.com/2073-4360/12/7/1590 |
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| author | Ilya Nifant’ev Alexander Vinogradov Alexey Vinogradov Stanislav Karchevsky Pavel Ivchenko |
| author_facet | Ilya Nifant’ev Alexander Vinogradov Alexey Vinogradov Stanislav Karchevsky Pavel Ivchenko |
| author_sort | Ilya Nifant’ev |
| collection | DOAJ |
| description | Zirconocene-catalyzed coordination oligomerization of higher α-olefins is of theoretical and practical interest. In this paper, we present the results of experimental and theoretical study of α-olefin oligomerization, catalyzed by (η<sup>5</sup>-C<sub>5</sub>H<sub>5</sub>)]<sub>2</sub>ZrX<sub>2</sub> <b>1</b>/<b>1′</b> and O[SiMe<sub>2</sub>(η<sup>5</sup>-C<sub>5</sub>H<sub>4</sub>)]<sub>2</sub>ZrX<sub>2</sub> <b>2</b>/<b>2′</b> (X = Cl, Me) with the activation by modified methylalymoxane MMAO-12 or by perfluoroalkyl borate [PhNMe<sub>2</sub>H][B(C<sub>6</sub>F<sub>5</sub>)<sub>4</sub>] (NB<sup>F</sup>) in the presence and in the absence of organoaluminium compounds, Al(CH<sub>2</sub>CHMe<sub>2</sub>)<sub>3</sub> (TIBA) and/or Et<sub>2</sub>AlCl. Under the conditions providing a conventional mononuclear reaction mechanism, <b>1′</b> catalyzed dimerization with low selectivity, while <b>2′</b> initiated the formation of oligomers in equal mass ratio. The presence of TIBA and especially Et<sub>2</sub>AlCl resulted in an increase of the selectivity of dimerization. Quantum chemical simulations of the main and side processes performed at the M-06x/ DGDZVP level of the density functional theory (DFT) allowed to explain experimental results involving traditional mononuclear and novel Zr-Al<sub>1</sub> and Zr-Al<sub>2</sub> mechanistic concepts. |
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| language | English |
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| spelling | doaj.art-627c0783df3c4c1a873c94b1e5b5529f2023-11-20T07:06:09ZengMDPI AGPolymers2073-43602020-07-01127159010.3390/polym12071590Experimental and Theoretical Study of Zirconocene-Catalyzed Oligomerization of 1-OcteneIlya Nifant’ev0Alexander Vinogradov1Alexey Vinogradov2Stanislav Karchevsky3Pavel Ivchenko4A.V. Topchiev Institute of Petrochemical Synthesis RAS, 29 Leninsky Pr., 119991 Moscow, RussiaA.V. Topchiev Institute of Petrochemical Synthesis RAS, 29 Leninsky Pr., 119991 Moscow, RussiaA.V. Topchiev Institute of Petrochemical Synthesis RAS, 29 Leninsky Pr., 119991 Moscow, RussiaJoint-Stock Company “Institute of Petroleum Refining and Petrochemistry”, 12 Iniciativnaya Str., 450065 Ufa, Republic of Bashkortostan, RussiaA.V. Topchiev Institute of Petrochemical Synthesis RAS, 29 Leninsky Pr., 119991 Moscow, RussiaZirconocene-catalyzed coordination oligomerization of higher α-olefins is of theoretical and practical interest. In this paper, we present the results of experimental and theoretical study of α-olefin oligomerization, catalyzed by (η<sup>5</sup>-C<sub>5</sub>H<sub>5</sub>)]<sub>2</sub>ZrX<sub>2</sub> <b>1</b>/<b>1′</b> and O[SiMe<sub>2</sub>(η<sup>5</sup>-C<sub>5</sub>H<sub>4</sub>)]<sub>2</sub>ZrX<sub>2</sub> <b>2</b>/<b>2′</b> (X = Cl, Me) with the activation by modified methylalymoxane MMAO-12 or by perfluoroalkyl borate [PhNMe<sub>2</sub>H][B(C<sub>6</sub>F<sub>5</sub>)<sub>4</sub>] (NB<sup>F</sup>) in the presence and in the absence of organoaluminium compounds, Al(CH<sub>2</sub>CHMe<sub>2</sub>)<sub>3</sub> (TIBA) and/or Et<sub>2</sub>AlCl. Under the conditions providing a conventional mononuclear reaction mechanism, <b>1′</b> catalyzed dimerization with low selectivity, while <b>2′</b> initiated the formation of oligomers in equal mass ratio. The presence of TIBA and especially Et<sub>2</sub>AlCl resulted in an increase of the selectivity of dimerization. Quantum chemical simulations of the main and side processes performed at the M-06x/ DGDZVP level of the density functional theory (DFT) allowed to explain experimental results involving traditional mononuclear and novel Zr-Al<sub>1</sub> and Zr-Al<sub>2</sub> mechanistic concepts.https://www.mdpi.com/2073-4360/12/7/1590coordination polymerizationdensity functional theorymethylenealkanesα-olefinsoligomerizationzirconocenes |
| spellingShingle | Ilya Nifant’ev Alexander Vinogradov Alexey Vinogradov Stanislav Karchevsky Pavel Ivchenko Experimental and Theoretical Study of Zirconocene-Catalyzed Oligomerization of 1-Octene Polymers coordination polymerization density functional theory methylenealkanes α-olefins oligomerization zirconocenes |
| title | Experimental and Theoretical Study of Zirconocene-Catalyzed Oligomerization of 1-Octene |
| title_full | Experimental and Theoretical Study of Zirconocene-Catalyzed Oligomerization of 1-Octene |
| title_fullStr | Experimental and Theoretical Study of Zirconocene-Catalyzed Oligomerization of 1-Octene |
| title_full_unstemmed | Experimental and Theoretical Study of Zirconocene-Catalyzed Oligomerization of 1-Octene |
| title_short | Experimental and Theoretical Study of Zirconocene-Catalyzed Oligomerization of 1-Octene |
| title_sort | experimental and theoretical study of zirconocene catalyzed oligomerization of 1 octene |
| topic | coordination polymerization density functional theory methylenealkanes α-olefins oligomerization zirconocenes |
| url | https://www.mdpi.com/2073-4360/12/7/1590 |
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