Decomposition pathways of Z-selective ruthenium metathesis catalysts.

نویسندگان

  • Myles B Herbert
  • Yu Lan
  • Benjamin K Keitz
  • Peng Liu
  • Koji Endo
  • Michael W Day
  • K N Houk
  • Robert H Grubbs
چکیده

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-H activated catalysts undergo decomposition via insertion of the alkylidene moiety into the chelating ruthenium-carbon 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.

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عنوان ژورنال:
  • Journal of the American Chemical Society

دوره 134 18  شماره 

صفحات  -

تاریخ انتشار 2012