Rate-Limiting Steps in the Intramolecular C–H Activation of Ruthenium N‑Heterocyclic Carbene Complexes

Ruthenium (II) complexes with N-heterocyclic carbenes (NHC) are commonly used as efficient catalysts in hydrogenation of olefins with simultaneous intramolecular C–H activation. Using the DFT approach, we have investigated the entire hydrogenation reaction pathway for four new potential catalysts and ethylene, a model substrate. Our calculations imply that the dissociation of phosphine is the rate-limiting step of hydrogenation, contrary to recent computational results. We also found that catalysts bearing NHCs with aliphatic and aromatic side groups are energetically favorable over other aliphatic cyclohexyl-substituted NHC. To examine how electronic properties of various catalysts influence the energetic barrier in the crucial steps of the reaction, we applied the Noncovalent Interaction analysis, which allowed us to reveal crucial interactions which stabilize/destabilize important intermediates and transition states in the hydrogenation reaction.