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| Verfasst von: | Pleßow, Philipp [VerfasserIn]  |
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| | Weigel, Laura Kathrin [VerfasserIn] |
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| | Lindner, Ronald [VerfasserIn] |
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| | Schäfer, Ansgar [VerfasserIn] |
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| | Rominger, Frank [VerfasserIn] |
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| | Limbach, Michael [VerfasserIn] |
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| | Hofmann, Peter [VerfasserIn] |
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| Titel: | Mechanistic details of the nickel-mediated formation of acrylates from CO2, ethylene and methyl iodide |
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| Verf.angabe: | Philipp N. Plessow, Laura Weigel, Ronald Lindner, Ansgar Schäfer, Frank Rominger, Michael Limbach, and Peter Hofmann |
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| E-Jahr: | 2013 |
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| Jahr: | May 28, 2013 |
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| Umfang: | 12 S. |
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| Fussnoten: | Gesehen am 02.12.2021 |
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| Titel Quelle: | Enthalten in: Organometallics |
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| Ort Quelle: | Washington, DC : ACS Publ., 1982 |
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| Jahr Quelle: | 2013 |
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| Band/Heft Quelle: | 32(2013), 11, Seite 3327-3338 |
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| ISSN Quelle: | 1520-6041 |
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| Abstract: | Methyl iodide induces the stoichiometric cleavage of nickelalactones, which are key intermediates in the nickel-mediated reaction of CO2 and alkenes to acrylates. Herein, we propose a modified and extended mechanism for this reaction on the basis of theoretical and experimental investigations for the bidentate P ligand 1,2-bis(di-tert-butylphosphino)ethane (dtbpe). The calculated elementary steps agree well with experimental findings: reaction barriers are reasonable and explain the facile liberation of acrylate from a nickelalactone by methyl iodide. We were able to isolate reactive intermediates and to verify the existence of proposed reaction pathways. Additionally, we have identified unproductive pathways leading to byproducts (e.g., propionates and catalytically inactive organometallic species). Although those side reactions can be suppressed to a certain extent, the strong binding of acrylate to nickel prevents a catalytic reaction, at least for the chosen ligand. |
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| DOI: | doi:10.1021/om400262b |
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| URL: | Bitte beachten Sie: Dies ist ein Bibliographieeintrag. Ein Volltextzugriff für Mitglieder der Universität besteht hier nur, falls für die entsprechende Zeitschrift/den entsprechenden Sammelband ein Abonnement besteht oder es sich um einen OpenAccess-Titel handelt.
Volltext ; Verlag: https://doi.org/10.1021/om400262b |
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| | Volltext: https://pubs.acs.org/doi/10.1021/om400262b |
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| | DOI: https://doi.org/10.1021/om400262b |
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| Datenträger: | Online-Ressource |
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| Sprache: | eng |
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| K10plus-PPN: | 1780094426 |
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| Verknüpfungen: | → Zeitschrift |
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Mechanistic details of the nickel-mediated formation of acrylates from CO2, ethylene and methyl iodide / Pleßow, Philipp [VerfasserIn]; May 28, 2013 (Online-Ressource)
