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Mechanism and Activity of Ruthenium Olefin Metathesis Catalysts

Sanford, Melanie S. and Love, Jennifer A. and Grubbs, Robert H. (2001) Mechanism and Activity of Ruthenium Olefin Metathesis Catalysts. Journal of the American Chemical Society, 123 (27). pp. 6543-6554. ISSN 0002-7863. https://resolver.caltech.edu/CaltechAUTHORS:20170406-142024439

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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.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1021/ja010624kDOIArticle
http://pubs.acs.org/doi/abs/10.1021/ja010624kPublisherArticle
http://pubs.acs.org/doi/suppl/10.1021/ja010624kPublisherSupporting Information
ORCID:
AuthorORCID
Sanford, Melanie S.0000-0001-9342-9436
Love, Jennifer A.0000-0003-2373-1036
Grubbs, Robert H.0000-0002-0057-7817
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.
Funders:
Funding AgencyGrant Number
NIH Predoctoral FellowshipUNSPECIFIED
NSFUNSPECIFIED
Issue or Number:27
Record Number:CaltechAUTHORS:20170406-142024439
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20170406-142024439
Official Citation:Mechanism and Activity of Ruthenium Olefin Metathesis Catalysts Melanie S. Sanford, Jennifer A. Love, and Robert H. Grubbs Journal of the American Chemical Society 2001 123 (27), 6543-6554 DOI: 10.1021/ja010624k
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:75812
Collection:CaltechAUTHORS
Deposited By: Ruth Sustaita
Deposited On:06 Apr 2017 21:54
Last Modified:03 Oct 2019 16:54

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