Possible Side Reactions Due to Water in Emulsion Polymerization by Late Transition Metal Complexes (II) : Deactivation of the Catalyst by a Wacker-Type Reaction

Lade...
Vorschaubild
Dateien
Datum
2005
Autor:innen
DeKock, Roger L.
Hristov, Iordan H.
Anderson, Grant D. W.
Ziegler, Tom
Herausgeber:innen
Kontakt
ISSN der Zeitschrift
Electronic ISSN
ISBN
Bibliografische Daten
Verlag
Schriftenreihe
Auflagebezeichnung
DOI (zitierfähiger Link)
ArXiv-ID
Internationale Patentnummer
Angaben zur Forschungsförderung
Projekt
Open Access-Veröffentlichung
Open Access Green
Core Facility der Universität Konstanz
Gesperrt bis
Titel in einer weiteren Sprache
Forschungsvorhaben
Organisationseinheiten
Zeitschriftenheft
Publikationstyp
Zeitschriftenartikel
Publikationsstatus
Published
Erschienen in
Organometallics. 2005, 24(11), pp. 2679-2687. ISSN 0276-7333. eISSN 1520-6041. Available under: doi: 10.1021/om049059v
Zusammenfassung

The transition metal catalyzed ethylene polymerization in water suspensions has been increasingly successful in the last couple of years. Water, however, adversely affects the polymerization process by deactivating the catalyst in a Wacker-type reaction. The cationic Pd(II)-diimine Brookhart catalyst 1 is studied here by a combination of quantum mechanics and molecular mechanics to determine the nature of the decomposition reaction. The study considers the decomposition process to take place in two stages. In the first stage, a coordinated olefin is attacked by a hydroxide group to ultimately produce a beta-hydroxy-ethyl complex 2. The second step represents a decomposition to acetaldehyde and Pd(0), the latter in the form of palladium black. For the attack of OH on the coordinated ethylene in 1, both an internal path involving transfer from a palladium-coordinated OH group produced from hydrolysis of a Pd-CH3 bond and an external path based on attack of H2O on coordinated ethylene were considered. Both paths are found to be feasible. For the second stage the most promising decomposition mode involves isomerization of 2 to the alpha-hydroxy-ethyl complex 5 followed by abstraction of a proton from the C-OH link to produce the Pd(0)-eta2-acetaldehyde complex 12. Finally, 12 releases acetaldehyde under the deposition of Pd(0) as palladium black.

Zusammenfassung in einer weiteren Sprache
Fachgebiet (DDC)
540 Chemie
Schlagwörter
Konferenz
Rezension
undefined / . - undefined, undefined
Zitieren
ISO 690DEKOCK, Roger L., Iordan H. HRISTOV, Grant D. W. ANDERSON, Inigo GÖTTKER-SCHNETMANN, Stefan MECKING, Tom ZIEGLER, 2005. Possible Side Reactions Due to Water in Emulsion Polymerization by Late Transition Metal Complexes (II) : Deactivation of the Catalyst by a Wacker-Type Reaction. In: Organometallics. 2005, 24(11), pp. 2679-2687. ISSN 0276-7333. eISSN 1520-6041. Available under: doi: 10.1021/om049059v
BibTex
@article{DeKock2005Possi-9823,
  year={2005},
  doi={10.1021/om049059v},
  title={Possible Side Reactions Due to Water in Emulsion Polymerization by Late Transition Metal Complexes (II) : Deactivation of the Catalyst by a Wacker-Type Reaction},
  number={11},
  volume={24},
  issn={0276-7333},
  journal={Organometallics},
  pages={2679--2687},
  author={DeKock, Roger L. and Hristov, Iordan H. and Anderson, Grant D. W. and Göttker-Schnetmann, Inigo and Mecking, Stefan and Ziegler, Tom}
}
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/123456789/9823">
    <dc:creator>Ziegler, Tom</dc:creator>
    <dc:creator>Anderson, Grant D. W.</dc:creator>
    <dc:contributor>Hristov, Iordan H.</dc:contributor>
    <dspace:isPartOfCollection rdf:resource="https://kops.uni-konstanz.de/server/rdf/resource/123456789/29"/>
    <dcterms:rights rdf:resource="http://creativecommons.org/licenses/by-nc-nd/2.0/"/>
    <dc:contributor>Mecking, Stefan</dc:contributor>
    <dc:format>application/pdf</dc:format>
    <dc:creator>Mecking, Stefan</dc:creator>
    <dc:date rdf:datatype="http://www.w3.org/2001/XMLSchema#dateTime">2011-03-24T18:14:39Z</dc:date>
    <dcterms:issued>2005</dcterms:issued>
    <dcterms:bibliographicCitation>First publ. in: Organometallics ; 24 (2005), 11. - S. 2679-2687</dcterms:bibliographicCitation>
    <dc:contributor>DeKock, Roger L.</dc:contributor>
    <dc:language>eng</dc:language>
    <dc:rights>Attribution-NonCommercial-NoDerivs 2.0 Generic</dc:rights>
    <void:sparqlEndpoint rdf:resource="http://localhost/fuseki/dspace/sparql"/>
    <dc:contributor>Göttker-Schnetmann, Inigo</dc:contributor>
    <dc:creator>Göttker-Schnetmann, Inigo</dc:creator>
    <dcterms:hasPart rdf:resource="https://kops.uni-konstanz.de/bitstream/123456789/9823/1/Possible_Side_Reactions_Due_to_Water_in_Emulsion2.pdf"/>
    <dc:creator>Hristov, Iordan H.</dc:creator>
    <dcterms:title>Possible Side Reactions Due to Water in Emulsion Polymerization by Late Transition Metal Complexes (II) : Deactivation of the Catalyst by a Wacker-Type Reaction</dcterms:title>
    <foaf:homepage rdf:resource="http://localhost:8080/"/>
    <dc:creator>DeKock, Roger L.</dc:creator>
    <dcterms:isPartOf rdf:resource="https://kops.uni-konstanz.de/server/rdf/resource/123456789/29"/>
    <dc:contributor>Anderson, Grant D. W.</dc:contributor>
    <bibo:uri rdf:resource="http://kops.uni-konstanz.de/handle/123456789/9823"/>
    <dcterms:abstract xml:lang="eng">The transition metal catalyzed ethylene polymerization in water suspensions has been increasingly successful in the last couple of years. Water, however, adversely affects the polymerization process by deactivating the catalyst in a Wacker-type reaction. The cationic Pd(II)-diimine Brookhart catalyst 1 is studied here by a combination of quantum mechanics and molecular mechanics to determine the nature of the decomposition reaction. The study considers the decomposition process to take place in two stages. In the first stage, a coordinated olefin is attacked by a hydroxide group to ultimately produce a beta-hydroxy-ethyl complex 2. The second step represents a decomposition to acetaldehyde and Pd(0), the latter in the form of palladium black. For the attack of OH on the coordinated ethylene in 1, both an internal path involving transfer from a palladium-coordinated OH group produced from hydrolysis of a Pd-CH3 bond and an external path based on attack of H2O on coordinated ethylene were considered. Both paths are found to be feasible. For the second stage the most promising decomposition mode involves isomerization of 2 to the alpha-hydroxy-ethyl complex 5 followed by abstraction of a proton from the C-OH link to produce the Pd(0)-eta2-acetaldehyde complex 12. Finally, 12 releases acetaldehyde under the deposition of Pd(0) as palladium black.</dcterms:abstract>
    <dc:contributor>Ziegler, Tom</dc:contributor>
    <dspace:hasBitstream rdf:resource="https://kops.uni-konstanz.de/bitstream/123456789/9823/1/Possible_Side_Reactions_Due_to_Water_in_Emulsion2.pdf"/>
  </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
Ja
Begutachtet
Diese Publikation teilen