ansa-titanocene catalysts for α-olefin polymerization : syntheses, structures, and reactions with methylaluminoxane and boron-based activators

Kurzanzeige
dc.contributor.authorBryliakov, Konstantin P.deu
dc.contributor.authorBabushkin, Dmitrii E.deu
dc.contributor.authorTalsi, Evgenii P.deu
dc.contributor.authorVoskoboynikov, Alexander Z.deu
dc.contributor.authorGritzo, Holgerdeu
dc.contributor.authorSchröder, Larsdeu
dc.contributor.authorDamrau, Hans-Robert H.deu
dc.contributor.authorWieser, Ulrichdeu
dc.contributor.authorSchaper, Frankdeu
dc.contributor.authorBrintzinger, Hans-Herbert
dc.date.accessioned2013-06-20T14:54:28Zdeu
dc.date.available2013-06-20T14:54:28Zdeu
dc.date.issued2005
dc.description.abstractThe racemic isomers of C2H4(1-Ind)2TiCl2 and Me2Si(2-Me-Benzind)2TiMe2 were synthesized and structurally characterized. Reactions of these and related ansa-titanocene complexes with methylaluminoxane or with the cationizing reagent [CPh3]+[B(C6F5)4]-/Al2Me6 were monitored by UV/vis, 1H NMR, and EPR methods. Under conditions approaching those typically used in olefin polymerizations, heterobinuclear cations of the type [DianTiIV(μ-Me)2AlMe2]+ (with Dian = bridged ligand dianion) dominate in each of these reaction systems, which catalyze the polymerization of propene at temperatures below ambient. Above 0 °C, these cations are reduced, mainly to neutral heterobinuclear species DianTiIII(μ-Me)2AlMe2, which appear to be inactive with regard to polymerization catalysis. In the absence of monomer, the main reducing agent appears to be ethyl aluminum admixtures in Al2Me6. Addition of monomer increases the rate of reduction rather drastically, probably via formation of titanium hydrides.eng
dc.description.versionpublished
dc.identifier.citationOrganometallics ; 24 (2005), 5. - S. 894-904deu
dc.identifier.doi10.1021/om0492496deu
dc.identifier.urihttp://kops.uni-konstanz.de/handle/123456789/23699
dc.language.isoengdeu
dc.legacy.dateIssued2013-06-20deu
dc.rightsterms-of-usedeu
dc.rights.urihttps://rightsstatements.org/page/InC/1.0/deu
dc.subject.ddc540deu
dc.titleansa-titanocene catalysts for α-olefin polymerization : syntheses, structures, and reactions with methylaluminoxane and boron-based activatorseng
dc.typeJOURNAL_ARTICLEdeu
dspace.entity.typePublication
kops.citation.bibtex
@article{Bryliakov2005ansat-23699,
  year={2005},
  doi={10.1021/om0492496},
  title={ansa-titanocene catalysts for α-olefin polymerization : syntheses, structures, and reactions with methylaluminoxane and boron-based activators},
  number={5},
  volume={24},
  issn={0276-7333},
  journal={Organometallics},
  pages={894--904},
  author={Bryliakov, Konstantin P. and Babushkin, Dmitrii E. and Talsi, Evgenii P. and Voskoboynikov, Alexander Z. and Gritzo, Holger and Schröder, Lars and Damrau, Hans-Robert H. and Wieser, Ulrich and Schaper, Frank and Brintzinger, Hans-Herbert}
}
kops.citation.iso690BRYLIAKOV, Konstantin P., Dmitrii E. BABUSHKIN, Evgenii P. TALSI, Alexander Z. VOSKOBOYNIKOV, Holger GRITZO, Lars SCHRÖDER, Hans-Robert H. DAMRAU, Ulrich WIESER, Frank SCHAPER, Hans-Herbert BRINTZINGER, 2005. ansa-titanocene catalysts for α-olefin polymerization : syntheses, structures, and reactions with methylaluminoxane and boron-based activators. In: Organometallics. 2005, 24(5), pp. 894-904. ISSN 0276-7333. eISSN 1520-6041. Available under: doi: 10.1021/om0492496deu
kops.citation.iso690BRYLIAKOV, Konstantin P., Dmitrii E. BABUSHKIN, Evgenii P. TALSI, Alexander Z. VOSKOBOYNIKOV, Holger GRITZO, Lars SCHRÖDER, Hans-Robert H. DAMRAU, Ulrich WIESER, Frank SCHAPER, Hans-Herbert BRINTZINGER, 2005. ansa-titanocene catalysts for α-olefin polymerization : syntheses, structures, and reactions with methylaluminoxane and boron-based activators. In: Organometallics. 2005, 24(5), pp. 894-904. ISSN 0276-7333. eISSN 1520-6041. Available under: doi: 10.1021/om0492496eng
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    <dcterms:abstract xml:lang="eng">The racemic isomers of C&lt;sub&gt;2&lt;/sub&gt;H&lt;sub&gt;4&lt;/sub&gt;(1-Ind)&lt;sub&gt;2&lt;/sub&gt;TiCl&lt;sub&gt;2&lt;/sub&gt; and Me&lt;sub&gt;2&lt;/sub&gt;Si(2-Me-Benzind)&lt;sub&gt;2&lt;/sub&gt;TiMe&lt;sub&gt;2&lt;/sub&gt; were synthesized and structurally characterized. Reactions of these and related ansa-titanocene complexes with methylaluminoxane or with the cationizing reagent [CPh&lt;sub&gt;3&lt;/sub&gt;]&lt;sup&gt;+&lt;/sup&gt;[B(C&lt;sub&gt;6&lt;/sub&gt;F&lt;sub&gt;5&lt;/sub&gt;)&lt;sub&gt;4&lt;/sub&gt;]&lt;sup&gt;-&lt;/sup&gt;/Al&lt;sub&gt;2&lt;/sub&gt;Me&lt;sub&gt;6&lt;/sub&gt; were monitored by UV/vis, &lt;sup&gt;1&lt;/sup&gt;H NMR, and EPR methods. Under conditions approaching those typically used in olefin polymerizations, heterobinuclear cations of the type [DianTiIV(μ-Me)&lt;sub&gt;2&lt;/sub&gt;AlMe&lt;sub&gt;2&lt;/sub&gt;]&lt;sup&gt;+&lt;/sup&gt; (with Dian = bridged ligand dianion) dominate in each of these reaction systems, which catalyze the polymerization of propene at temperatures below ambient. Above 0 °C, these cations are reduced, mainly to neutral heterobinuclear species DianTiIII(μ-Me)&lt;sub&gt;2&lt;/sub&gt;AlMe&lt;sub&gt;2&lt;/sub&gt;, which appear to be inactive with regard to polymerization catalysis. In the absence of monomer, the main reducing agent appears to be ethyl aluminum admixtures in Al&lt;sub&gt;2&lt;/sub&gt;Me&lt;sub&gt;6&lt;/sub&gt;. Addition of monomer increases the rate of reduction rather drastically, probably via formation of titanium hydrides.</dcterms:abstract>
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kops.identifier.nbnurn:nbn:de:bsz:352-236997deu
kops.sourcefieldOrganometallics. 2005, <b>24</b>(5), pp. 894-904. ISSN 0276-7333. eISSN 1520-6041. Available under: doi: 10.1021/om0492496deu
kops.sourcefield.plainOrganometallics. 2005, 24(5), pp. 894-904. ISSN 0276-7333. eISSN 1520-6041. Available under: doi: 10.1021/om0492496deu
kops.sourcefield.plainOrganometallics. 2005, 24(5), pp. 894-904. ISSN 0276-7333. eISSN 1520-6041. Available under: doi: 10.1021/om0492496eng
kops.submitter.emailoleg.kozlov@uni-konstanz.dedeu
relation.isAuthorOfPublicationab4c86da-5c57-43c2-83ff-89fe2e461f70
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source.bibliographicInfo.volume24
source.identifier.eissn1520-6041deu
source.identifier.issn0276-7333
source.periodicalTitleOrganometallics

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