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The Isomerization Equilibrium between Cis and Trans Chloride Ruthenium Olefin Metathesis Catalysts from Quantum Mechanics Calculations

Benitez, Diego and Goddard, William A., III (2005) The Isomerization Equilibrium between Cis and Trans Chloride Ruthenium Olefin Metathesis Catalysts from Quantum Mechanics Calculations. Journal of the American Chemical Society, 127 (35). pp. 12218-12219. ISSN 0002-7863. https://resolver.caltech.edu/CaltechAUTHORS:20170512-133829737

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Abstract

The cis−trans chloride isomerization of a ruthenium olefin metathesis catalyst is studied using quantum mechanics (B3LYP DFT), including the Poisson−Boltzmann (PBF) continuum approximation. The predicted geometries agree with experiment. The energies in methylene chloride, lead to ΔG = −0.70 kcal/mol and a cis:trans ratio of 76:24, quite close to the experimental value of ΔG = −0.78 kcal/mol or c:t 78:22. In contrast, we predict that in benzene c:t = 4:96 in agreement with the experimental observation of only the trans isomer. Our calculated relative activation energies explain the observed difference in initiation rates and suggest that each isomer should be isolable in high ratio by simply changing solvent.


Item Type:Article
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http://dx.doi.org/10.1021/ja051796aDOIArticle
http://pubs.acs.org/doi/abs/10.1021/ja051796aPublisherArticle
http://pubs.acs.org/doi/suppl/10.1021/ja051796aRelated ItemSupporting Information
ORCID:
AuthorORCID
Goddard, William A., III0000-0003-0097-5716
Additional Information:© 2005 American Chemical Society. Received 21 March 2005. Published online 16 August 2005. Published in print 1 September 2005. The facilities of the Materials and Process Simulation Center are supported by ONR-DURIP, ARO-DURIP, MURI-ARO, MURI-ONR, DOE (ASC, FETL), NSF (CHE), NIH, Aventis Pharma, ChevronTexaco, Nissan Corp., Berlex Biopharma, and Beckman Institute.
Funders:
Funding AgencyGrant Number
Office of Naval Research (ONR)UNSPECIFIED
Army Research Office (ARO)UNSPECIFIED
Department of Energy (DOE)UNSPECIFIED
NSFUNSPECIFIED
NIHUNSPECIFIED
Aventis PharmaUNSPECIFIED
ChevronTexacoUNSPECIFIED
Nissan Corp.UNSPECIFIED
Berlex BiopharmaUNSPECIFIED
Caltech Beckman InstituteUNSPECIFIED
Issue or Number:35
Record Number:CaltechAUTHORS:20170512-133829737
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20170512-133829737
Official Citation:The Isomerization Equilibrium between Cis and Trans Chloride Ruthenium Olefin Metathesis Catalysts from Quantum Mechanics Calculations Diego Benitez and William A. Goddard, III Journal of the American Chemical Society 2005 127 (35), 12218-12219 DOI: 10.1021/ja051796a
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:77421
Collection:CaltechAUTHORS
Deposited By: Ruth Sustaita
Deposited On:12 May 2017 22:57
Last Modified:03 Oct 2019 17:57

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