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 deve...
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Published in | Organometallics Vol. 36; no. 20; pp. 3940 - 3953 |
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Main Authors | , , , |
Format | Journal Article |
Language | English |
Published |
WASHINGTON
American Chemical Society
23.10.2017
Amer Chemical Soc |
Subjects | |
Online Access | Get full text |
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Summary: | 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. |
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ISSN: | 0276-7333 1520-6041 |
DOI: | 10.1021/acs.organomet.7b00555 |