The influence of the cationic carbenes on the initiation kinetics of ruthenium-based metathesis catalysts; a DFT study.

Cationic carbenes are a relatively new and rare group of ancillary ligands, which have shown their superior activity in a number of challenging catalytic reactions. In ruthenium-based metathesis catalysis they are often used as ammonium tags, to provide water-soluble, environment-friendly catalysts. In this work we performed computational studies on three cationic carbenes with the formal positive charge located at different distances from the carbene carbon. We show that the predicted initiation rates of Grubbs, indenylidene, and Hoveyda-Grubbs-like complexes incorporating these carbenes show little variance and are similar to initiation rates of standard Grubbs, indenylidene, and Hoveyda-Grubbs catalysts. In all investigated cases the partial charge of the carbene carbon atom is similar, resulting in comparable C-Ru bond strengths and Ru-P/O dissociation Gibbs free energies.