| Publication type: | Article in scientific journal |
| Type of review: | Peer review (publication) |
| Title: | Mechanism and activity of ruthenium olefin metathesis catalysts : the role of ligands and substrates from a theoretical perspective |
| Authors: | Adlhart, Christian Chen, Peter |
| DOI: | 10.1021/ja0305757 |
| Published in: | Journal of the American Chemical Society |
| Volume(Issue): | 126 |
| Issue: | 11 |
| Page(s): | 3496 |
| Pages to: | 3510 |
| Issue Date: | 25-Feb-2004 |
| Publisher / Ed. Institution: | American Chemical Society |
| ISSN: | 0002-7863 1520-5126 |
| Language: | English |
| Subjects: | Metathesis catalysts; Reaction mechanism; Alkene reactions; Density functional theory |
| Subject (DDC): | 540: Chemistry |
| Abstract: | 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 |
| Fulltext version: | Published version |
| License (according to publishing contract): | Licence according to publishing contract |
| Departement: | Life Sciences and Facility Management |
| Organisational Unit: | Institute of Chemistry and Biotechnology (ICBT) |
| Appears in collections: | 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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