Publikationstyp: | Beitrag in wissenschaftlicher Zeitschrift |
Art der Begutachtung: | Peer review (Publikation) |
Titel: | Mechanism and activity of ruthenium olefin metathesis catalysts : the role of ligands and substrates from a theoretical perspective |
Autor/-in: | Adlhart, Christian Chen, Peter |
DOI: | 10.1021/ja0305757 |
Erschienen in: | Journal of the American Chemical Society |
Band(Heft): | 126 |
Heft: | 11 |
Seite(n): | 3496 |
Seiten bis: | 3510 |
Erscheinungsdatum: | 25-Feb-2004 |
Verlag / Hrsg. Institution: | American Chemical Society |
ISSN: | 0002-7863 1520-5126 |
Sprache: | Englisch |
Schlagwörter: | Metathesis catalysts; Reaction mechanism; Alkene reactions; Density functional theory |
Fachgebiet (DDC): | 540: Chemie |
Zusammenfassung: | The reaction mechanism of olefin metathesis by ruthenium carbene catalysts is studied by gradient-corrected density functional calculations (BP86). Alternative reaction mechanisms for the reaction of the “first-generation” Grubbs-type catalyst (PCy3)2Cl2Ru=CH2 (1) for the reaction with ethylene are studied. The most likely dissociative mechanism with trans olefin coordination is investigated for the metathesis reaction between the “first-” and the “second-generation” Grubbs-type catalysts 1 and (H2IMes)(PCy3)Cl2Ru=CH2 (2) with different substrates, ethylene, ethyl vinyl ether, and norbornene, and a profound influence of the substrate is found. In contrast to the degenerate reaction with ethylene, the reactions with ethyl vinyl ether and norbornene are strongly exergonic by 8-15 kcal/mol, and this excess energy is released after passing through the metallacyclobutane structure. While the metallacyclobutane is in a deep potential minimum for degenerate metathesis reactions, the energy barrier for the [2+2] cycloreversion vanishes for the most exergonic reactions. On the free energy surface under typical experimental conditions, the rate-limiting steps for the overall reactions are then either metallacyclobutane formation for 1 or phosphane ligand dissociation for 2. |
URI: | https://digitalcollection.zhaw.ch/handle/11475/2100 |
Volltext Version: | Publizierte Version |
Lizenz (gemäss Verlagsvertrag): | Lizenz gemäss Verlagsvertrag |
Departement: | Life Sciences und Facility Management |
Organisationseinheit: | Institut für Chemie und Biotechnologie (ICBT) |
Enthalten in den Sammlungen: | Publikationen Life Sciences und Facility Management |
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Adlhart, C., & Chen, P. (2004). Mechanism and activity of ruthenium olefin metathesis catalysts : the role of ligands and substrates from a theoretical perspective. Journal of the American Chemical Society, 126(11), 3496–3510. https://doi.org/10.1021/ja0305757
Adlhart, C. and Chen, P. (2004) ‘Mechanism and activity of ruthenium olefin metathesis catalysts : the role of ligands and substrates from a theoretical perspective’, Journal of the American Chemical Society, 126(11), pp. 3496–3510. Available at: https://doi.org/10.1021/ja0305757.
C. Adlhart and P. Chen, “Mechanism and activity of ruthenium olefin metathesis catalysts : the role of ligands and substrates from a theoretical perspective,” Journal of the American Chemical Society, vol. 126, no. 11, pp. 3496–3510, Feb. 2004, doi: 10.1021/ja0305757.
ADLHART, Christian und Peter CHEN, 2004. Mechanism and activity of ruthenium olefin metathesis catalysts : the role of ligands and substrates from a theoretical perspective. Journal of the American Chemical Society. 25 Februar 2004. Bd. 126, Nr. 11, S. 3496–3510. DOI 10.1021/ja0305757
Adlhart, Christian, and Peter Chen. 2004. “Mechanism and Activity of Ruthenium Olefin Metathesis Catalysts : The Role of Ligands and Substrates from a Theoretical Perspective.” Journal of the American Chemical Society 126 (11): 3496–3510. https://doi.org/10.1021/ja0305757.
Adlhart, Christian, and Peter Chen. “Mechanism and Activity of Ruthenium Olefin Metathesis Catalysts : The Role of Ligands and Substrates from a Theoretical Perspective.” Journal of the American Chemical Society, vol. 126, no. 11, Feb. 2004, pp. 3496–510, https://doi.org/10.1021/ja0305757.
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