Decomposition Pathways of Z-Selective Ruthenium Metathesis Catalysts
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- 作者：Myles B. Herbert ; Yu Lan ; Benjamin K. Keitz ; Peng Liu ; Koji Endo ; Michael W. Day ; K. N. Houk ; Robert H. Grubbs
- 刊名：The Journal of the American Chemical Society
- 出版年：2012
- 出版时间：May 9, 2012
- 年：2012
- 卷：134
- 期：18
- 页码：7861-7866
- 全文大小：410K
- 年卷期：v.134,no.18(May 9, 2012)
- ISSN：1520-5126
文摘
The decomposition of a Z-selective ruthenium metathesis catalyst and structurally similar analogues has been investigated utilizing X-ray crystallography and density functional theory. Isolated X-ray crystal structures suggest that recently reported C鈥揌 activated catalysts undergo decomposition via insertion of the alkylidene moiety into the chelating ruthenium鈥揷arbon bond followed by hydride elimination, which is supported by theoretical calculations. The resulting ruthenium hydride intermediates have been implicated in previously observed olefin migration, and thus lead to unwanted byproducts in cross metathesis reactions. Preventing these decomposition modes will be essential in the design of more active and selective Z-selective catalysts.