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Published October 23, 2017 | Supplemental Material
Journal Article Open

Synthesis and Evaluation of Sterically Demanding Ruthenium Dithiolate Catalysts for Stereoretentive Olefin Metathesis


Dithiolate ligands have recently been used in ruthenium-catalyzed olefin metathesis and have provided access to a kinetically E selective pathway through stereoretentive olefin metathesis. The typical dithiolate used is relatively simple with low steric demands imparted on the catalyst. We have developed a synthetic route that allows access to sterically demanding dithiolate ligands. The catalysts generated provided a pathway to study the intricate structure–activity relationships in olefin metathesis. It was found that DFT calculations can predict the ligand arrangement around the ruthenium center with remarkable accuracy. These dithiolate catalysts proved resistant to ligand isomerization and were stable even under forcing conditions. Additionally, catalyst initiation and olefin metathesis studies delivered a better understanding to the interplay between dithiolate ligand structure and catalyst activity and selectivity.

Additional Information

© 2017 American Chemical Society. Received: July 23, 2017. Publication Date (Web): October 9, 2017. The authors thank the Office of Naval Research (N00014-14-1-0650) and the Arnold and Mabel Beckman Foundation (T.P.M.) for funding. Dr. David VanderVeld is thanked for assistance with NMR experimentation. Dr. Michael W. Day and Larry M. Henling are thanked for X-ray crystallographic analysis. The Bruker KAPPA APEXII X-ray diffractometer was purchased via an NSF CRIF:MU award to the California Institute of Technology (CHE-0639094). Materia, Inc., is thanked for a generous donation of GH-II and 711. Dr. Tzu-Pin Lin and Dr. Allegra Liberman-Martin are thanked for assistance with catalyst initiation experiments. Tonia S. Ahmed and Dr. Noah F. Fine Nathel are thanked for helpful discussions.

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August 19, 2023
October 17, 2023