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Catalytic Properties of Zirconocene-Based Systems in 1-Hexene Oligomerization and Structure of Metal Hydride Reaction Centers

Despite large-scale investigations of homogeneous single-site metallocene catalysts and systems based on them, there are still unsolved problems related to the control of their activity and chemo- and stereoselectivity. A solution to these problems is required to develop efficient methods for the sy...

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Autores principales: Parfenova, Lyudmila V., Kovyazin, Pavel V., Bikmeeva, Almira Kh., Palatov, Eldar R., Ivchenko, Pavel V., Nifant’ev, Ilya E., Khalilov, Leonard M.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: MDPI 2023
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10058051/
https://www.ncbi.nlm.nih.gov/pubmed/36985393
http://dx.doi.org/10.3390/molecules28062420
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author Parfenova, Lyudmila V.
Kovyazin, Pavel V.
Bikmeeva, Almira Kh.
Palatov, Eldar R.
Ivchenko, Pavel V.
Nifant’ev, Ilya E.
Khalilov, Leonard M.
author_facet Parfenova, Lyudmila V.
Kovyazin, Pavel V.
Bikmeeva, Almira Kh.
Palatov, Eldar R.
Ivchenko, Pavel V.
Nifant’ev, Ilya E.
Khalilov, Leonard M.
author_sort Parfenova, Lyudmila V.
collection PubMed
description Despite large-scale investigations of homogeneous single-site metallocene catalysts and systems based on them, there are still unsolved problems related to the control of their activity and chemo- and stereoselectivity. A solution to these problems is required to develop efficient methods for the synthesis of practically useful products of alkene transformations, such as dimers, oligomers, and polymers. Here we studied the catalytic activity of structurally diverse zirconocenes (L(2)ZrCl(2), L = Cp, C(5)Me(5), Ind, L(2) = Me(2)CCp(2), Me(2)SiCp(2), Me(2)C(2)Cp(2), rac-Me(2)CInd(2), rac-H(4)C(2)Ind(2), BIPh(Ind)(2), H(4)C(2)[THInd](2)), and co-catalysts activating the system, namely HAlBu(i)(2), MMAO-12, and (Ph(3)C)[B(C(6)F(5))(4)], at low activator/Zr ratios in a 1-hexene oligomerization reaction. The influence of catalyst structure and system composition on the alkene conversion, the type of products, and the reaction stereoselectivity were investigated. The composition of hydride intermediates formed in the L(2)ZrCl(2)–HAlBu(i)(2)–activator system (L(2) = ansa-Me(2)CCp(2), Ind) was studied by NMR spectroscopy. Participation of the bis-zirconium hydride complex as the precursor of catalytically active sites of the alkene dimerization reaction was shown.
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spelling pubmed-100580512023-03-30 Catalytic Properties of Zirconocene-Based Systems in 1-Hexene Oligomerization and Structure of Metal Hydride Reaction Centers Parfenova, Lyudmila V. Kovyazin, Pavel V. Bikmeeva, Almira Kh. Palatov, Eldar R. Ivchenko, Pavel V. Nifant’ev, Ilya E. Khalilov, Leonard M. Molecules Article Despite large-scale investigations of homogeneous single-site metallocene catalysts and systems based on them, there are still unsolved problems related to the control of their activity and chemo- and stereoselectivity. A solution to these problems is required to develop efficient methods for the synthesis of practically useful products of alkene transformations, such as dimers, oligomers, and polymers. Here we studied the catalytic activity of structurally diverse zirconocenes (L(2)ZrCl(2), L = Cp, C(5)Me(5), Ind, L(2) = Me(2)CCp(2), Me(2)SiCp(2), Me(2)C(2)Cp(2), rac-Me(2)CInd(2), rac-H(4)C(2)Ind(2), BIPh(Ind)(2), H(4)C(2)[THInd](2)), and co-catalysts activating the system, namely HAlBu(i)(2), MMAO-12, and (Ph(3)C)[B(C(6)F(5))(4)], at low activator/Zr ratios in a 1-hexene oligomerization reaction. The influence of catalyst structure and system composition on the alkene conversion, the type of products, and the reaction stereoselectivity were investigated. The composition of hydride intermediates formed in the L(2)ZrCl(2)–HAlBu(i)(2)–activator system (L(2) = ansa-Me(2)CCp(2), Ind) was studied by NMR spectroscopy. Participation of the bis-zirconium hydride complex as the precursor of catalytically active sites of the alkene dimerization reaction was shown. MDPI 2023-03-07 /pmc/articles/PMC10058051/ /pubmed/36985393 http://dx.doi.org/10.3390/molecules28062420 Text en © 2023 by the authors. https://creativecommons.org/licenses/by/4.0/Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license (https://creativecommons.org/licenses/by/4.0/).
spellingShingle Article
Parfenova, Lyudmila V.
Kovyazin, Pavel V.
Bikmeeva, Almira Kh.
Palatov, Eldar R.
Ivchenko, Pavel V.
Nifant’ev, Ilya E.
Khalilov, Leonard M.
Catalytic Properties of Zirconocene-Based Systems in 1-Hexene Oligomerization and Structure of Metal Hydride Reaction Centers
title Catalytic Properties of Zirconocene-Based Systems in 1-Hexene Oligomerization and Structure of Metal Hydride Reaction Centers
title_full Catalytic Properties of Zirconocene-Based Systems in 1-Hexene Oligomerization and Structure of Metal Hydride Reaction Centers
title_fullStr Catalytic Properties of Zirconocene-Based Systems in 1-Hexene Oligomerization and Structure of Metal Hydride Reaction Centers
title_full_unstemmed Catalytic Properties of Zirconocene-Based Systems in 1-Hexene Oligomerization and Structure of Metal Hydride Reaction Centers
title_short Catalytic Properties of Zirconocene-Based Systems in 1-Hexene Oligomerization and Structure of Metal Hydride Reaction Centers
title_sort catalytic properties of zirconocene-based systems in 1-hexene oligomerization and structure of metal hydride reaction centers
topic Article
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10058051/
https://www.ncbi.nlm.nih.gov/pubmed/36985393
http://dx.doi.org/10.3390/molecules28062420
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