Publikation:

Promotion of Selective Pathways in Isomerizing Functionalization of Plant Oils by Rigid Framework Substituents

Vorschaubild

Dateien

Christl_0-264112.pdf
Christl_0-264112.pdfGröße: 395.5 KBDownloads: 451

Datum

2014

Autor:innen

Cavallo, Luigi

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:352-0-264112
DOI (zitierfähiger Link)
https://doi.org/10.1002/cssc.201402441
ArXiv-ID

Internationale Patentnummer

Link zur Lizenz
Urheberrechtlich geschützt

Angaben zur Forschungsförderung

Projekt

Open Access-Veröffentlichung
Open Access Green

Sammlungen

Chemie: Publikationen
Core Facility der Universität Konstanz

Gesperrt bis

Titel in einer weiteren Sprache

Publikationstyp
Zeitschriftenartikel
Publikationsstatus
Published

Erschienen in

ChemSusChem. 2014, 7(12), pp. 3491-3495. ISSN 1864-5631. eISSN 1864-564X. Available under: doi: 10.1002/cssc.201402441

Zusammenfassung

The 1,2-(CH2P(1-adamantyl)2)2C6H4 (dadpx) coordinated palladium complex [(dadpx)Pd(OTf)2] (1) is a catalyst precursor for the isomerizing methoxycarbonylation of the internal double bond of methyl oleate, with an unprecedented selectivity (96 %) for the linear diester 1,19-dimethyl nonadecanedioate. Rapid formation of the catalytically active solvent-coordinated hydride species [(dadpx)PdH(MeOH)]+ (3-MeOH) is evidenced by NMR spectroscopy, and further isolation and X-ray crystal structure analysis of [(dadpx)PdH(PPh3)]+ (3-PPh3). DFT calculations of key steps of the catalytic cycle unravel methanolysis as the decisive step for enhanced selectivity and the influence of the rigid adamantyl framework on this step by destabilization of transition states of unselective pathways.

Zusammenfassung in einer weiteren Sprache

Fachgebiet (DDC)
540 Chemie

Schlagwörter

Konferenz

Rezension
undefined / . - undefined, undefined

Forschungsvorhaben

Organisationseinheiten

Zeitschriftenheft

Zugehörige Datensätze in KOPS

Zitieren

ISO 690CHRISTL, Josefine, Philipp ROESLE, Florian STEMPFLE, Gerhard MÜLLER, Lucia CAPORASO, Luigi CAVALLO, Stefan MECKING, 2014. Promotion of Selective Pathways in Isomerizing Functionalization of Plant Oils by Rigid Framework Substituents. In: ChemSusChem. 2014, 7(12), pp. 3491-3495. ISSN 1864-5631. eISSN 1864-564X. Available under: doi: 10.1002/cssc.201402441
BibTex
@article{Christl2014Promo-29371,
  year={2014},
  doi={10.1002/cssc.201402441},
  title={Promotion of Selective Pathways in Isomerizing Functionalization of Plant Oils by Rigid Framework Substituents},
  number={12},
  volume={7},
  issn={1864-5631},
  journal={ChemSusChem},
  pages={3491--3495},
  author={Christl, Josefine and Roesle, Philipp and Stempfle, Florian and Müller, Gerhard and Caporaso, Lucia and Cavallo, Luigi and Mecking, Stefan}
}
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/123456789/29371">
    <void:sparqlEndpoint rdf:resource="http://localhost/fuseki/dspace/sparql"/>
    <dc:language>eng</dc:language>
    <dc:date rdf:datatype="http://www.w3.org/2001/XMLSchema#dateTime">2014-12-02T09:46:29Z</dc:date>
    <dc:rights>terms-of-use</dc:rights>
    <dc:creator>Stempfle, Florian</dc:creator>
    <dcterms:available rdf:datatype="http://www.w3.org/2001/XMLSchema#dateTime">2014-12-02T09:46:29Z</dcterms:available>
    <dc:contributor>Caporaso, Lucia</dc:contributor>
    <dcterms:rights rdf:resource="https://rightsstatements.org/page/InC/1.0/"/>
    <dc:contributor>Stempfle, Florian</dc:contributor>
    <dspace:hasBitstream rdf:resource="https://kops.uni-konstanz.de/bitstream/123456789/29371/1/Christl_0-264112.pdf"/>
    <dc:creator>Cavallo, Luigi</dc:creator>
    <dcterms:abstract xml:lang="eng">The 1,2-(CH&lt;sub&gt;2&lt;/sub&gt;P(1-adamantyl)&lt;sub&gt;2&lt;/sub&gt;)&lt;sub&gt;2&lt;/sub&gt;C&lt;sub&gt;6&lt;/sub&gt;H&lt;sub&gt;4&lt;/sub&gt; (dadpx) coordinated palladium complex [(dadpx)Pd(OTf)&lt;sub&gt;2&lt;/sub&gt;] (1) is a catalyst precursor for the isomerizing methoxycarbonylation of the internal double bond of methyl oleate, with an unprecedented selectivity (96 %) for the linear diester 1,19-dimethyl nonadecanedioate. Rapid formation of the catalytically active solvent-coordinated hydride species [(dadpx)PdH(MeOH)]&lt;sup&gt;+&lt;/sup&gt; (3-MeOH) is evidenced by NMR spectroscopy, and further isolation and X-ray crystal structure analysis of [(dadpx)PdH(PPh3)]&lt;sup&gt;+&lt;/sup&gt; (3-PPh&lt;sub&gt;3&lt;/sub&gt;). DFT calculations of key steps of the catalytic cycle unravel methanolysis as the decisive step for enhanced selectivity and the influence of the rigid adamantyl framework on this step by destabilization of transition states of unselective pathways.</dcterms:abstract>
    <dc:creator>Mecking, Stefan</dc:creator>
    <dc:creator>Müller, Gerhard</dc:creator>
    <foaf:homepage rdf:resource="http://localhost:8080/"/>
    <dcterms:issued>2014</dcterms:issued>
    <dspace:isPartOfCollection rdf:resource="https://kops.uni-konstanz.de/server/rdf/resource/123456789/29"/>
    <bibo:uri rdf:resource="http://kops.uni-konstanz.de/handle/123456789/29371"/>
    <dc:contributor>Müller, Gerhard</dc:contributor>
    <dc:creator>Caporaso, Lucia</dc:creator>
    <dc:contributor>Mecking, Stefan</dc:contributor>
    <dc:contributor>Roesle, Philipp</dc:contributor>
    <dcterms:hasPart rdf:resource="https://kops.uni-konstanz.de/bitstream/123456789/29371/1/Christl_0-264112.pdf"/>
    <dc:creator>Roesle, Philipp</dc:creator>
    <dcterms:isPartOf rdf:resource="https://kops.uni-konstanz.de/server/rdf/resource/123456789/29"/>
    <dcterms:title>Promotion of Selective Pathways in Isomerizing Functionalization of Plant Oils by Rigid Framework Substituents</dcterms:title>
    <dc:creator>Christl, Josefine</dc:creator>
    <dc:contributor>Cavallo, Luigi</dc:contributor>
    <dc:contributor>Christl, Josefine</dc:contributor>
  </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