title: Decomposition pathways of Z-selective ruthenium metathesis catalysts.
abstract: 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.
authors.affiliation: Arnold and Mabel Beckman Laboratory of Chemical Synthesis, Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, California 91125, USA.
authors.forename: Myles B
authors.initials: MB
authors.lastname: Herbert
authors.forename: Yu
authors.initials: Y
authors.lastname: Lan
authors.forename: Benjamin K
authors.initials: BK
authors.lastname: Keitz
authors.forename: Peng
authors.initials: P
authors.lastname: Liu
authors.forename: Koji
authors.initials: K
authors.lastname: Endo
authors.forename: Michael W
authors.initials: MW
authors.lastname: Day
authors.forename: K N
authors.initials: KN
authors.lastname: Houk
authors.forename: Robert H
authors.initials: RH
authors.lastname: Grubbs
mesh_terms: D000475:Alkenes / Q000138:chemical synthesis*; D002384:Catalysis; D002614:Chelating Agents / Q000737:chemistry; D056831:Coordination Complexes / Q000737:chemistry*; D018360:Crystallography, X-Ray; D008958:Models, Molecular; D011789:Quantum Theory; D012428:Ruthenium / Q000737:chemistry*
chemical_list: D000475:Alkenes; D002614:Chelating Agents; D056831:Coordination Complexes; D012428:Ruthenium