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Synthesis, Structure, and Activity of Enhanced Initiators for Olefin Metathesis

Love, Jennifer A. and Sanford, Melanie S. and Day, Michael W. and Grubbs, Robert H. (2003) Synthesis, Structure, and Activity of Enhanced Initiators for Olefin Metathesis. Journal of the American Chemical Society, 125 (33). pp. 10103-10109. ISSN 0002-7863.

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A series of ruthenium olefin metathesis catalysts of the general structure (H_2IMes)(PR_3)(Cl)_2Ru CHPh (H_2IMes = 1,3-dimesityl-4,5-dihydroimidazol-2-ylidene) have been prepared; these complexes are readily accessible in two steps from commercially available (H_2IMes)(PCy_3)(Cl)_2Ru CHPh. Their phosphine dissociation rate constants (k_1), relative rates of phosphine reassociation, and relative reaction rates in ring-opening metathesis polymerization (ROMP) and ring-closing metathesis (RCM) have been investigated. The rates of phosphine dissociation (initiation) from these complexes increase with decreasing phosphine donor strength. Complexes containing a triarylphosphine exhibit dramatically improved initiation relative to (H_2IMes)(PCy_3)(Cl)_2Ru CHPh. Conversely, phosphine reassociation shows no direct correlation with phosphine electronics. In general, increased phosphine dissociation leads to faster olefin metathesis reaction rates, which is of direct significance to both organic and polymer metathesis processes.

Item Type:Article
Related URLs:
URLURL TypeDescription Information
Love, Jennifer A.0000-0003-2373-1036
Sanford, Melanie S.0000-0001-9342-9436
Grubbs, Robert H.0000-0002-0057-7817
Additional Information:© 2003 American Chemical Society. Received June 26, 2002. Publication Date (Web): July 23, 2003. The authors would like to thank Lawrence M. Henling (X-ray crystallography), Tina M. Trnka, John P. Morgan, and D. William Ward for helpful discussions and Materia, Inc., for a generous supply of complex 2. J.A.L. thanks the National Institutes of Health for a postdoctoral fellowship. This work was supported by the National Science Foundation.
Funding AgencyGrant Number
NIH Postdoctoral FellowshipUNSPECIFIED
Issue or Number:33
Record Number:CaltechAUTHORS:20170405-140506647
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Official Citation:Synthesis, Structure, and Activity of Enhanced Initiators for Olefin Metathesis Jennifer A. Love, Melanie S. Sanford, Michael W. Day, and Robert H. Grubbs Journal of the American Chemical Society 2003 125 (33), 10103-10109 DOI: 10.1021/ja027472t
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:75740
Deposited By: Tony Diaz
Deposited On:05 Apr 2017 21:19
Last Modified:03 Oct 2019 16:53

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