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Published April 17, 2013 | Supplemental Material + Accepted Version
Journal Article Open

Z-Selective Ethenolysis with a Ruthenium Metathesis Catalyst: Experiment and Theory


The Z-selective ethenolysis activity of chelated ruthenium metathesis catalysts was investigated with experiment and theory. A five-membered chelated catalyst that was successfully employed in Z-selective cross metathesis reactions has now been found to be highly active for Z-selective ethenolysis at low ethylene pressures, while tolerating a wide variety of functional groups. This phenomenon also affects its activity in cross metathesis reactions and prohibits crossover reactions of internal olefins via trisubstituted ruthenacyclobutane intermediates. In contrast, a related catalyst containing a six-membered chelated architecture is not active for ethenolysis and seems to react through different pathways more reminiscent of previous generations of ruthenium catalysts. Computational investigations of the effects of substitution on relevant transition states and ruthenacyclobutane intermediates revealed that the differences of activities are attributed to the steric repulsions of the anionic ligand with the chelating groups.

Additional Information

© 2013 American Chemical Society. Received: January 29, 2013; Published: April 2, 2013; Published In Issue April 17, 2013. Dr. David VanderVelde is thanked for his assistance with NMR characterization and experiments. This work was financially supported by the NIH (NIH 5R01GM031332-27, R.H.G.), the NSF (CHE-1048404, R.H.G. and CHE-1059084, K.N.H.), the NDSEG (fellowship to B.K.K.), and Mitsubishi Tanabe Pharma Corporation (H.M.). Materia, Inc. is acknowledged for its generous donation of metathesis catalysts. Calculations were performed on the Hoffman2 cluster at UCLA and the Extreme Science and Engineering Discovery Environment (XSEDE), which is supported by the National Science Foundation (OCI-1053575).

Attached Files

Accepted Version - nihms464028.pdf

Supplemental Material - ja4010267_si_001.pdf

Supplemental Material - ja4010267_si_002.pdf


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