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Decomposition Pathways of Z-Selective Ruthenium Metathesis Catalysts

Herbert, Myles B. and Lan, Yu and Keitz, Benjamin K. and Liu, Peng and Endo, Koji and Day, Michael W. and Houk, K. N. and Grubbs, Robert H. (2012) Decomposition Pathways of Z-Selective Ruthenium Metathesis Catalysts. Journal of the American Chemical Society, 134 (18). pp. 7861-7866. ISSN 0002-7863. PMCID PMC3375820. https://resolver.caltech.edu/CaltechAUTHORS:20120611-090301040

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Abstract

The decomposition of a Z-selective ruthenium metathesis catalyst and structurally similar analogues has been investigated utilizing X-ray crystallography and density functional theory. Isolated X-ray crystal structures suggest that recently reported C–H activated catalysts undergo decomposition via insertion of the alkylidene moiety into the chelating ruthenium–carbon bond followed by hydride elimination, which is supported by theoretical calculations. The resulting ruthenium hydride intermediates have been implicated in previously observed olefin migration, and thus lead to unwanted byproducts in cross metathesis reactions. Preventing these decomposition modes will be essential in the design of more active and selective Z-selective catalysts.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1021/ja301108mDOIArticle
http://pubs.acs.org/doi/abs/10.1021/ja301108mPublisherArticle
https://www.ncbi.nlm.nih.gov/pmc/articles/PMC3375820/PubMed CentralArticle
ORCID:
AuthorORCID
Liu, Peng0000-0002-8188-632X
Houk, K. N.0000-0002-8387-5261
Grubbs, Robert H.0000-0002-0057-7817
Additional Information:© 2012 American Chemical Society. Published In Issue: May 09, 2012; Article ASAP: April 26, 2012; Just Accepted Manuscript:April 13, 2012; Received: February 02, 2012. This work is dedicated to the memory of Dr. Michael W. Day. Dr. David VanderVelde is thanked for his assistance with NMR characterization and experiments. Lawrence Henling is acknowledged for X-ray crystallographic analysis. 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.), Mitsui Chemicals, Inc. (K.E.), and the NDSEG (fellowship to B.K.K.). The Bruker KAPPA APEXII Xray diffractometer was purchased via an NSF CRIF:MU award to the California Institute of Technology (CHE-0639094). 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).
Funders:
Funding AgencyGrant Number
NIH5R01GM031332-27
NSFCHE-1048404
NSFCHE-1059084
Mitsui Chemicals, Inc.UNSPECIFIED
National Defense Science and Engineering Graduate (NDSEG) FellowshipUNSPECIFIED
NSFCHE-0639094
NSFOCI-1053575
Issue or Number:18
PubMed Central ID:PMC3375820
Record Number:CaltechAUTHORS:20120611-090301040
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20120611-090301040
Official Citation:Decomposition Pathways of Z-Selective Ruthenium Metathesis Catalysts Myles B. Herbert, Yu Lan, Benjamin K. Keitz, Peng Liu, Koji Endo, Michael W. Day, K. N. Houk, and Robert H. Grubbs Journal of the American Chemical Society 2012 134 (18), 7861-7866
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:31868
Collection:CaltechAUTHORS
Deposited By: Jason Perez
Deposited On:12 Jun 2012 20:58
Last Modified:03 Oct 2019 03:55

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