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dc.contributor.authorAdlhart, Christian-
dc.contributor.authorChen, Peter-
dc.date.accessioned2018-01-17T13:22:13Z-
dc.date.available2018-01-17T13:22:13Z-
dc.date.issued2004-02-25-
dc.identifier.issn0002-7863de_CH
dc.identifier.issn1520-5126de_CH
dc.identifier.urihttps://digitalcollection.zhaw.ch/handle/11475/2100-
dc.description.abstractThe 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.de_CH
dc.language.isoende_CH
dc.publisherAmerican Chemical Societyde_CH
dc.relation.ispartofJournal of the American Chemical Societyde_CH
dc.rightsLicence according to publishing contractde_CH
dc.subjectMetathesis catalystsde_CH
dc.subjectReaction mechanismde_CH
dc.subjectAlkene reactionsde_CH
dc.subjectDensity functional theoryde_CH
dc.subject.ddc540: Chemiede_CH
dc.titleMechanism and activity of ruthenium olefin metathesis catalysts : the role of ligands and substrates from a theoretical perspectivede_CH
dc.typeBeitrag in wissenschaftlicher Zeitschriftde_CH
dcterms.typeTextde_CH
zhaw.departementLife Sciences und Facility Managementde_CH
zhaw.organisationalunitInstitut für Chemie und Biotechnologie (ICBT)de_CH
dc.identifier.doi10.1021/ja0305757de_CH
zhaw.funding.euNode_CH
zhaw.issue11de_CH
zhaw.originated.zhawYesde_CH
zhaw.pages.end3510de_CH
zhaw.pages.start3496de_CH
zhaw.publication.statuspublishedVersionde_CH
zhaw.volume126de_CH
zhaw.publication.reviewPeer review (Publikation)de_CH
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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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