Publikation:

Alkylaluminum-complexed zirconocene hydrides : identification of hydride-bridged species by NMR spectroscopy

Vorschaubild

Dateien

Zu diesem Dokument gibt es keine Dateien.

Datum

2008

Autor:innen

Baldwin, Steven M.
Bercaw, John E.

Herausgeber:innen

Kontakt

ISSN der Zeitschrift

Electronic ISSN

ISBN

Bibliografische Daten

Verlag

Schriftenreihe

Auflagebezeichnung

URI (zitierfähiger Link)
http://nbn-resolving.de/urn:nbn:de:bsz:352-236622
DOI (zitierfähiger Link)
https://doi.org/10.1021/ja8054723
ArXiv-ID

Internationale Patentnummer

Angaben zur Forschungsförderung

Projekt

Open Access-Veröffentlichung

Sammlungen

Chemie: Publikationen
Core Facility der Universität Konstanz

Gesperrt bis

Titel in einer weiteren Sprache

Publikationstyp
Zeitschriftenartikel
Publikationsstatus
Published

Erschienen in

Journal of the American Chemical Society. 2008, 130(51), pp. 17423-17433. ISSN 0002-7863. eISSN 1520-5126. Available under: doi: 10.1021/ja8054723

Zusammenfassung

Reactions of unbridged zirconocene dichlorides, (RnC5H5−n)2ZrCl2 (n = 0, 1, or 2), with diisobutylaluminum hydride (HAliBu2) result in the formation of tetranuclear trihydride clusters of the type (RnC5H5−n)2Zr(μ-H)3(AliBu2)3(μ-Cl)2, which contain three [AliBu2] units. Ring-bridged ansa-zirconocene dichlorides, Me2E(RnC5H4−n)2ZrCl2 with E = C or Si, on the other hand, are found to form binuclear dihydride complexes of the type Me2E(RnC5H4−n)2Zr(Cl)(μ-H)2AliBu2 with only one [AliBu2] unit. The dichotomy between unbridged and bridged zirconocene derivatives with regard to tetranuclear versus binuclear product formation is proposed to be connected to different degrees of rotational freedom of their C5-ring ligands. Alkylaluminum-complexed zirconocene dihydrides, previously observed in zirconocene-based precatalyst systems activated by methylalumoxane (MAO) upon addition of HAliBu2 or AliBu3, are proposed to be species of the type Me2Si(ind)2Zr(Me)(μ-H)2AliBu2, stabilized by interaction of their terminal Me group with a Lewis acidic site of MAO.

Zusammenfassung in einer weiteren Sprache

Fachgebiet (DDC)
540 Chemie

Schlagwörter

Konferenz

Rezension
undefined / . - undefined, undefined

Forschungsvorhaben

Organisationseinheiten

Zeitschriftenheft

Zugehörige Datensätze in KOPS

Zitieren

ISO 690BALDWIN, Steven M., John E. BERCAW, Hans-Herbert BRINTZINGER, 2008. Alkylaluminum-complexed zirconocene hydrides : identification of hydride-bridged species by NMR spectroscopy. In: Journal of the American Chemical Society. 2008, 130(51), pp. 17423-17433. ISSN 0002-7863. eISSN 1520-5126. Available under: doi: 10.1021/ja8054723
BibTex
@article{Baldwin2008-12-24Alkyl-23662,
  year={2008},
  doi={10.1021/ja8054723},
  title={Alkylaluminum-complexed zirconocene hydrides : identification of hydride-bridged species by NMR spectroscopy},
  number={51},
  volume={130},
  issn={0002-7863},
  journal={Journal of the American Chemical Society},
  pages={17423--17433},
  author={Baldwin, Steven M. and Bercaw, John E. and Brintzinger, Hans-Herbert}
}
RDF
<rdf:RDF
    xmlns:dcterms="http://purl.org/dc/terms/"
    xmlns:dc="http://purl.org/dc/elements/1.1/"
    xmlns:rdf="http://www.w3.org/1999/02/22-rdf-syntax-ns#"
    xmlns:bibo="http://purl.org/ontology/bibo/"
    xmlns:dspace="http://digital-repositories.org/ontologies/dspace/0.1.0#"
    xmlns:foaf="http://xmlns.com/foaf/0.1/"
    xmlns:void="http://rdfs.org/ns/void#"
    xmlns:xsd="http://www.w3.org/2001/XMLSchema#" > 
  <rdf:Description rdf:about="https://kops.uni-konstanz.de/server/rdf/resource/123456789/23662">
    <dcterms:issued>2008-12-24</dcterms:issued>
    <dc:creator>Bercaw, John E.</dc:creator>
    <dc:contributor>Baldwin, Steven M.</dc:contributor>
    <void:sparqlEndpoint rdf:resource="http://localhost/fuseki/dspace/sparql"/>
    <bibo:uri rdf:resource="http://kops.uni-konstanz.de/handle/123456789/23662"/>
    <dcterms:abstract xml:lang="eng">Reactions of unbridged zirconocene dichlorides, (R&lt;sub&gt;n&lt;/sub&gt;C&lt;sub&gt;5&lt;/sub&gt;H&lt;sub&gt;5−n&lt;/sub&gt;)&lt;sub&gt;2&lt;/sub&gt;ZrCl&lt;sub&gt;2&lt;/sub&gt; (n = 0, 1, or 2), with diisobutylaluminum hydride (HAl&lt;sup&gt;i&lt;/sup&gt;Bu&lt;sub&gt;2&lt;/sub&gt;) result in the formation of tetranuclear trihydride clusters of the type (R&lt;sub&gt;n&lt;/sub&gt;C&lt;sub&gt;5&lt;/sub&gt;H&lt;sub&gt;5−n&lt;/sub&gt;)&lt;sub&gt;2&lt;/sub&gt;Zr(μ-H)&lt;sub&gt;3&lt;/sub&gt;(Al&lt;sup&gt;i&lt;/sup&gt;Bu&lt;sub&gt;2&lt;/sub&gt;)&lt;sub&gt;3&lt;/sub&gt;(μ-Cl)&lt;sub&gt;2&lt;/sub&gt;, which contain three [Al&lt;sup&gt;i&lt;/sup&gt;Bu&lt;sub&gt;2&lt;/sub&gt;] units. Ring-bridged ansa-zirconocene dichlorides, Me&lt;sub&gt;2&lt;/sub&gt;E(R&lt;sub&gt;n&lt;/sub&gt;C&lt;sub&gt;5&lt;/sub&gt;H&lt;sub&gt;4−n&lt;/sub&gt;)&lt;sub&gt;2&lt;/sub&gt;ZrCl&lt;sub&gt;2&lt;/sub&gt; with E = C or Si, on the other hand, are found to form binuclear dihydride complexes of the type Me&lt;sub&gt;2&lt;/sub&gt;E(R&lt;sub&gt;n&lt;/sub&gt;C&lt;sub&gt;5&lt;/sub&gt;H&lt;sub&gt;4−n&lt;/sub&gt;)&lt;sub&gt;2&lt;/sub&gt;Zr(Cl)(μ-H)&lt;sub&gt;2&lt;/sub&gt;Al&lt;sup&gt;i&lt;/sup&gt;Bu&lt;sub&gt;2&lt;/sub&gt; with only one [Al&lt;sup&gt;i&lt;/sup&gt;Bu&lt;sub&gt;2&lt;/sub&gt;] unit. The dichotomy between unbridged and bridged zirconocene derivatives with regard to tetranuclear versus binuclear product formation is proposed to be connected to different degrees of rotational freedom of their C&lt;sub&gt;5&lt;/sub&gt;-ring ligands. Alkylaluminum-complexed zirconocene dihydrides, previously observed in zirconocene-based precatalyst systems activated by methylalumoxane (MAO) upon addition of HAl&lt;sup&gt;i&lt;/sup&gt;Bu&lt;sub&gt;2&lt;/sub&gt; or Al&lt;sup&gt;i&lt;/sup&gt;Bu&lt;sub&gt;3&lt;/sub&gt;, are proposed to be species of the type Me&lt;sub&gt;2&lt;/sub&gt;Si(ind)&lt;sub&gt;2&lt;/sub&gt;Zr(Me)(μ-H)&lt;sub&gt;2&lt;/sub&gt;Al&lt;sup&gt;i&lt;/sup&gt;Bu&lt;sub&gt;2&lt;/sub&gt;, stabilized by interaction of their terminal Me group with a Lewis acidic site of MAO.</dcterms:abstract>
    <dcterms:isPartOf rdf:resource="https://kops.uni-konstanz.de/server/rdf/resource/123456789/29"/>
    <dc:creator>Baldwin, Steven M.</dc:creator>
    <dc:rights>terms-of-use</dc:rights>
    <dc:language>eng</dc:language>
    <dcterms:title>Alkylaluminum-complexed zirconocene hydrides : identification of hydride-bridged species by NMR spectroscopy</dcterms:title>
    <dc:contributor>Brintzinger, Hans-Herbert</dc:contributor>
    <foaf:homepage rdf:resource="http://localhost:8080/"/>
    <dspace:isPartOfCollection rdf:resource="https://kops.uni-konstanz.de/server/rdf/resource/123456789/29"/>
    <dc:contributor>Bercaw, John E.</dc:contributor>
    <dc:date rdf:datatype="http://www.w3.org/2001/XMLSchema#dateTime">2013-06-19T14:22:29Z</dc:date>
    <dcterms:available rdf:datatype="http://www.w3.org/2001/XMLSchema#dateTime">2013-06-19T14:22:29Z</dcterms:available>
    <dcterms:bibliographicCitation>Journal of American Chemical Society ; 130 (2008), 51. - S. 17423-17433</dcterms:bibliographicCitation>
    <dc:creator>Brintzinger, Hans-Herbert</dc:creator>
    <dcterms:rights rdf:resource="https://rightsstatements.org/page/InC/1.0/"/>
  </rdf:Description>
</rdf:RDF>

Interner Vermerk

xmlui.Submission.submit.DescribeStep.inputForms.label.kops_note_fromSubmitter

Kontakt
URL der Originalveröffentl.

Prüfdatum der URL

Prüfungsdatum der Dissertation

Finanzierungsart

Kommentar zur Publikation

Allianzlizenz
Corresponding Authors der Uni Konstanz vorhanden
Internationale Co-Autor:innen
Universitätsbibliographie
Begutachtet
Diese Publikation teilen