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Stereochemistry of first monomer insertion into a metal-methyl bond : enantioselectivity and diastereoselectivity in 3-methyl 1-pentene polymerization with metallocene catalysts

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1997

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Sacchi, Maria Carmela
Barsties, Elke
Tritto, Incoronata
Locatelli, Paolo
Stehling, Udo

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Macromolecules. 1997, 30(5), pp. 1267-1271. ISSN 0024-9297. eISSN 1520-5835. Available under: doi: 10.1021/ma9609801

Zusammenfassung

The stereochemistry of first monomer insertion in the polymerization of racemic 3-methyl-1-pentene ((RS)-3MP1) with three different metallocene complexes, Me2Si(Ind)2ZrCl2 (I), Me2Si(BenzInd)2ZrCl2 (II), and Me2Si(MeBenzInd)2ZrCl2 (III), in the presence of MAO/Al(13CH3)3 cocatalyst has been studied and the results have been compared to those previously obtained using the traditional isospecific TiCl3/Al(13CH3)3 heterogeneous catalyst. The highest enantioselectivity and diastereoselectivity are observed with the least hindered metallocene (catalyst I). While enantioselectivity decreases due to benzannelation of the ligand with catalyst II, the methyl substitution in the 2-position of the cyclopentadienyl rings with catalyst III causes an almost complete lack of diastereoselectivity.

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540 Chemie

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ISO 690SACCHI, Maria Carmela, Elke BARSTIES, Incoronata TRITTO, Paolo LOCATELLI, Hans-Herbert BRINTZINGER, Udo STEHLING, 1997. Stereochemistry of first monomer insertion into a metal-methyl bond : enantioselectivity and diastereoselectivity in 3-methyl 1-pentene polymerization with metallocene catalysts. In: Macromolecules. 1997, 30(5), pp. 1267-1271. ISSN 0024-9297. eISSN 1520-5835. Available under: doi: 10.1021/ma9609801
BibTex
@article{Sacchi1997Stere-23758,
  year={1997},
  doi={10.1021/ma9609801},
  title={Stereochemistry of first monomer insertion into a metal-methyl bond : enantioselectivity and diastereoselectivity in 3-methyl 1-pentene polymerization with metallocene catalysts},
  number={5},
  volume={30},
  issn={0024-9297},
  journal={Macromolecules},
  pages={1267--1271},
  author={Sacchi, Maria Carmela and Barsties, Elke and Tritto, Incoronata and Locatelli, Paolo and Brintzinger, Hans-Herbert and Stehling, Udo}
}
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    <dcterms:abstract xml:lang="eng">The stereochemistry of first monomer insertion in the polymerization of racemic 3-methyl-1-pentene ((RS)-3MP1) with three different metallocene complexes, Me&lt;sub&gt;2&lt;/sub&gt;Si(Ind)&lt;sub&gt;2&lt;/sub&gt;ZrCl&lt;sub&gt;2&lt;/sub&gt; (I), Me&lt;sub&gt;2&lt;/sub&gt;Si(BenzInd)&lt;sub&gt;2&lt;/sub&gt;ZrCl&lt;sub&gt;2&lt;/sub&gt; (II), and Me&lt;sub&gt;2&lt;/sub&gt;Si(MeBenzInd)&lt;sub&gt;2&lt;/sub&gt;ZrCl&lt;sub&gt;2&lt;/sub&gt; (III), in the presence of MAO/Al(13CH3)3 cocatalyst has been studied and the results have been compared to those previously obtained using the traditional isospecific TiCl&lt;sub&gt;3&lt;/sub&gt;/Al(&lt;sup&gt;13&lt;/sup&gt;CH&lt;sub&gt;3&lt;/sub&gt;)&lt;sub&gt;3&lt;/sub&gt; heterogeneous catalyst. The highest enantioselectivity and diastereoselectivity are observed with the least hindered metallocene (catalyst I). While enantioselectivity decreases due to benzannelation of the ligand with catalyst II, the methyl substitution in the 2-position of the cyclopentadienyl rings with catalyst III causes an almost complete lack of diastereoselectivity.</dcterms:abstract>
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