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Published February 3, 2016 | Supplemental Material
Journal Article Open

Probing Stereoselectivity in Ring-Opening Metathesis Polymerization Mediated by Cyclometalated Ruthenium-Based Catalysts: A Combined Experimental and Computational Study


The microstructures of polymers produced by ring-opening metathesis polymerization (ROMP) with cyclometalated Ru-carbene metathesis catalysts were investigated. A strong bias for a cis,syndiotactic microstructure with minimal head-to-tail bias was observed. In instances where trans errors were introduced, it was determined that these regions were also syndiotactic. Furthermore, hypothetical reaction intermediates and transition structures were analyzed computationally. Combined experimental and computational data support a reaction mechanism in which cis,syndio-selectivity is a result of stereogenic metal control, while microstructural errors are predominantly due to alkylidene isomerization via rotation about the Ru═C double bond.

Additional Information

© 2016 American Chemical Society. Received: November 24, 2015. Publication Date (Web): January 4, 2016. We thank Dr. David VanderVelde for his assistance with NMR experimentation and analysis. This work was financially supported by the NIH (R01GM031332), ONR (N000141310895), NSF (CHE-1361104, K.N.H.), NDSEG (fellowship to L.E.R.), NSF-GRFP (fellowship to T.S.A.), and NSERC (fellowship to V.M.M.). Materia, Inc. is thanked 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 NSF (OCI-1053575). The authors declare no competing financial interest.

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