Direct Observation of a 14-Electron Ruthenacyclobutane Relevant to Olefin Metathesis
- 17 March 2005
- journal article
- research article
- Published by American Chemical Society (ACS) in Journal of the American Chemical Society
- Vol. 127 (14), 5032-5033
- https://doi.org/10.1021/ja042259d
Abstract
The 14-electron ruthenium phosphonium alkylidene complex [(IH2Mes)Cl2RuCH(PCy3)][B(C6F5)4], 1b, a highly active olefin metathesis catalyst, reacts with stoichiometric quantities of ethylene at −50 °C in CD2Cl2 to generate the ruthenacyclobutane complex [(IH2Mes)Cl2RuCH2CH2CH2], 2, and [CH2CH(PCy3)][B(C6F5)4] in quantitative yield by NMR spectroscopy. 1H and 13C NMR spectroscopies on 2 and 2-13C3 are consistent with a symmetrical C2v structure, providing the first experimental information concerning this crucial intermediate in ruthenium-mediated olefin metathesis. At −50 °C, exchange with free ethylene takes place on the chemical time scale. Complex 2 decomposes in solution upon warming to room temperature, generating propene and unknown ruthenium product(s).Keywords
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