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Published June 27, 2007 | Supplemental Material
Journal Article Open

Decomposition of Ruthenium Olefin Metathesis Catalysts


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.

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.

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Supplemental Material - ja0713577si20070405_014614.pdf


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