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Decomposition of Ruthenium Olefin Metathesis Catalysts

Hong, Soon Hyeok and Wenzel, Anna G. and Salguero, Tina T. and Day, Michael W. and Grubbs, Robert H. (2007) Decomposition of Ruthenium Olefin Metathesis Catalysts. Journal of the American Chemical Society, 129 (25). pp. 7961-7968. ISSN 0002-7863. http://resolver.caltech.edu/CaltechAUTHORS:20170516-081139547

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Abstract

The decomposition of a series of ruthenium metathesis catalysts has been examined using methylidene species as model complexes. All of the phosphine-containing methylidene complexes decomposed to generate methylphosphonium salts, and their decomposition routes followed first-order kinetics. The formation of these salts in high conversion, coupled with the observed kinetic behavior for this reaction, suggests that the major decomposition pathway involves nucleophilic attack of a dissociated phosphine on the methylidene carbon. This mechanism also is consistent with decomposition observed in the presence of ethylene as a model olefin substrate. The decomposition of phosphine-free catalyst (H_2IMes)(Cl)_2Ru CH(2-C_6H_4-O-i-Pr) (H_2IMes = 1,3-dimesityl-4,5-dihydroimidazol-2-ylidene) with ethylene was found to generate unidentified ruthenium hydride species. The novel ruthenium complex (H_2IMes)(pyridine)_3(Cl)_2Ru, which was generated during the synthetic attempts to prepare the highly unstable pyridine-based methylidene complex (H_2IMes)(pyridine)_2(Cl)_2Ru CH_2, is also reported.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1021/ja0713577DOIArticle
http://pubs.acs.org/doi/abs/10.1021/ja0713577PublisherArticle
http://pubs.acs.org/doi/suppl/10.1021/ja0713577PublisherSupporting Information
ORCID:
AuthorORCID
Hong, Soon Hyeok0000-0003-0605-9735
Grubbs, Robert H.0000-0002-0057-7817
Additional Information:© 2007 American Chemical Society. Received February 26, 2007. Publication Date (Web): June 5, 2007. The authors thank Dr. Mona Shahgholi for the mass spectrometric analyses, Lawrence M. Henling for contributions to the X-ray crystallography, and Andrew Hejl for generous donation of complex 25. Materia, Inc. is acknowledged for generous donation of ruthenium catalysts 1−3. Postdoctoral funding for A.G.W. was provided by the NIH (NRSA GM070147-02) and UNCF-Pfizer. This work was supported by the National Science Foundation.
Funders:
Funding AgencyGrant Number
NIH Predoctoral FellowshipGM070147-02
UNCF-PfizerUNSPECIFIED
NSFUNSPECIFIED
Record Number:CaltechAUTHORS:20170516-081139547
Persistent URL:http://resolver.caltech.edu/CaltechAUTHORS:20170516-081139547
Official Citation:Decomposition of Ruthenium Olefin Metathesis Catalysts Soon Hyeok Hong, Anna G. Wenzel, Tina T. Salguero, Michael W. Day, and Robert H. Grubbs Journal of the American Chemical Society 2007 129 (25), 7961-7968 DOI: 10.1021/ja0713577
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:77485
Collection:CaltechAUTHORS
Deposited By: Tony Diaz
Deposited On:16 May 2017 15:59
Last Modified:16 May 2017 15:59

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