Related Experiment Video
Updated: Jul 11, 2026

The Synthesis, Characterization and Reactivity of a Series of Ruthenium N-triphosPh Complexes
Published on: April 10, 2015
Mechanism of Ru(II)-catalyzed olefin insertion and C-H activation from quantum chemical studies
Jonas Oxgaard1, William A Goddard
1Materials and Process Simulation Center, Beckman Institute (139-74), Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, California 91125, USA.
Abstract:
The mechanism of catalytic hydroarylation of olefins by the homogeneous Ru(Tp)(CO)(Ph)(NCCH3) catalyst recently reported by Gunnoe et al. is characterized using quantum mechanics (density functional theory). The catalytic cycle features two key steps, 1,2-olefin insertion and C-H activation via an unusual mechanism, oxidative hydrogen migration. We find that these two key steps are competitive and that improving the rate of one step is detrimental to the rate of the other. The Ru catalyst has better balance and consequently higher activity than the previously explored Ir-based system.
Related Concept Videos
Catalysis
Reduction of Alkynes to cis-Alkenes: Catalytic Hydrogenation
Like alkenes, alkynes can be reduced to alkanes in the presence of transition metal catalysts such as Pt, Pd, or Ni. The reaction involves two sequential syn additions of hydrogen via a cis-alkene intermediate.
Photochemical Electrocyclic Reactions: Stereochemistry
Selection Rules: Photochemical Activation
Cycloaddition Reactions: MO Requirements for Photochemical Activation
Catalysis
Heterogeneous Catalysis

