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Published May 9, 2012 | Accepted Version + Supplemental Material
Journal Article Open

Decomposition Pathways of Z-Selective Ruthenium Metathesis Catalysts

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.

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).

Attached Files

Accepted Version - nihms371414.pdf

Supplemental Material - ja301108m_si_001.pdf

Supplemental Material - ja301108m_si_002.cif

Supplemental Material - ja301108m_si_003.cif

Supplemental Material - ja301108m_si_004.cif

Supplemental Material - ja301108m_si_005.cif

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Created:
August 19, 2023
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October 17, 2023