Olefin metathesis can be exploited to build unique carbon-carbon bonds with potential applications in the chemical, pharmaceutical, and polymer industries. Currently, much effort is focused on designing efficient vanadium catalysts as cheaper and abundant alternatives to the traditional molybdenum, ruthenium and tungsten-based catalysts. A vanadium alkylidene catalyst containing an aryloxide donor ligand, two trimethyl phosphine ligands, a trimethylslilane and a bisisopropyl-substituted arylimido group has been reported to exhibit high activity and selectivity in olefin metathesis reactions. However, rapid decomposition and deactivation of the catalyst with time has also been observed.   The proposed decomposition pathway for the vanadium alkylidene catalyst via β-hydride elimination, which hinders catalytic efficiency during productive metathesis, is explored with density functional theory. These results suggest that the vanadium catalyst containing fluoro-substituted aryloxide ligands is more prone to degradation than the corresponding catalyst with chloro-substituted aryloxide ligands. Comparing the free energy barriers in β-hydride elimination and productive metathesis for both systems will provide insights into how such ligand modifications can be used to favor the productive process over degradation.

Vanadium alkylidene catalysts for olefin metathesis

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