Mechanism and Activity of Ruthenium Olefin Metathesis Catalysts
Abstract
This report details the effects of ligand variation on the mechanism and activity of ruthenium-based olefin metathesis catalysts. A series of ruthenium complexes of the general formula L(PR_3)(X)_2Ru ═ CHR^1 have been prepared, and the influence of the substituents L, X, R, and R^1 on the rates of phosphine dissociation and initiation as well as overall activity for olefin metathesis reactions was examined. In all cases, initiation proceeds by dissociative substitution of a phosphine ligand (PR_3) with an olefinic substrate. All of the ligands L, X, R, and R^1 have a significant impact on initiation rates and on catalyst activity. The origins of the observed substituent effects as well as the implications of these studies for the design and implementation of new olefin metathesis catalysts and substrates are discussed in detail.
Additional Information
© 2001 American Chemical Society. Received 8 March 2001. Published online 16 June 2001. Published in print 1 July 2001. The authors would like to thank Dr. Jeff Yoder and Dr. Ola Wendt for assistance with magnetization transfer experiments. Dr. Michael Ulman and Annita Zhong are acknowledged for helpful discussions, and Dr. Steven Goldberg and Dr. Jon Seiders are acknowledged for critical reading of this manuscript. J.A.L. thanks the NIH for a postdoctoral fellowship. This work was supported by the NSF.Attached Files
Supplemental Material - ja010624k_s.pdf
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Additional details
- Eprint ID
- 75812
- DOI
- 10.1021/ja010624k
- Resolver ID
- CaltechAUTHORS:20170406-142024439
- NIH Predoctoral Fellowship
- NSF
- Created
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2017-04-06Created from EPrint's datestamp field
- Updated
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2021-11-15Created from EPrint's last_modified field