The reaction path for the formation of a binuclear hydrido-acrylate complex in a CO2-C2H4 coupling process is explored in detail by locating the key intermediates and transition states on model potential energy surfaces derived from density functional calculations on realistic models. The formation of the new C-C bond is shown to take place via oxidative coupling of coordinated CO2 and C2H4 ligands resulting in a metalla-lactone intermediate, which can rearrange to an agostic species allowing for a β-hydrogen shift process. The overall reaction is predicted to be clearly exothermic with all intermediates lying below the reactants in energy, and the highest barrier steps correspond to C-C coupling and β-hydrogen transfer. The phosphine ligands are found to play an important role in various phases of the reaction as their dissociation controls the coordination of CO2, the formation of the agostic intermediate, and the dimerization process; furthermore, their presence facilitates the oxidative coupling by supplying electrons to the metal center. Our results provide a theoretical support for the reaction mechanism proposed from experimental observations. The effect of the solvent medium on the relative energy of reaction intermediates and transition states is examined and found important in order to predict reliable energetics.
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