JOURNAL OF PHYSICAL CHEMISTRY A, vol.112, no.20, pp.4636-4643, 2008 (SCI-Expanded)
A catalytic system-consisting of tungsten carbene generated from WCl6 and an atomic carbon is investigated theoretically for the metathesis of 1-octene at B3LYP/extended LANL2DZ level of DFT. The ground-state geometries and charge distributions of the structures belonging to the reaction mechanism are located. Energetics for the complete set of reactions, involving the formation of the tungsten carbene precatalyst, Cl4W=CCl2, the formation of tungsten methylidene and tungsten heptylidene with this precatalyst, and finally productive and degenerative metathesis steps with these alkylidene species are calculated in terms of total electronic energy and thermal energies. The free-energy (Delta G(298)) surfaces of the structures involved in the related reactions are constructed. In addition, solvent effects on the single point energies of the structures are investigated for two different solvents, namely, cyclohexane and chloroform. The results indicate that the formation of the catalytically active heptylidene is energetically favored in comparison to the formation of methylidene, while the degenerative and productive metathesis steps are competitive. In the catalytic cycle, the formation of ethylene is exothermic, while the formation of 7-tetradecene is endothermic. As expected, solvent effects on the metathesis reactions are minor and solvation does not cause any change in the directions of the overall metathesis reactions.