The Isomerization Equilibrium between Cis and Trans Chloride Ruthenium Olefin Metathesis Catalysts from Quantum Mechanics Calculations
- Creators
- Benitez, Diego
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Goddard, William A., III
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.
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.Attached Files
Supplemental Material - ja051796asi20050331_035255.pdf
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Additional details
- Eprint ID
- 77421
- Resolver ID
- CaltechAUTHORS:20170512-133829737
- Office of Naval Research (ONR)
- Army Research Office (ARO)
- Department of Energy (DOE)
- NSF
- NIH
- Aventis Pharma
- ChevronTexaco
- Nissan Corp.
- Berlex Biopharma
- Caltech Beckman Institute
- Created
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2017-05-12Created from EPrint's datestamp field
- Updated
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2021-11-15Created from EPrint's last_modified field