Density Functional Study of the Reppe Carbonylation of Acetylene

The Reppe carbonylation of acetylene has been investigated by both static and dynamic density functional methods. Structures of all intermediates and transition states involved in each step of the catalytic cycle have been determined using gradient-corrected exchange-correlation potentials. Dynamic simulations have been performed on the migrative insertion of CO into the metal-vinyl bond after CO coordination by the metal and show that the insertion is preceded by a Berry pseudorotation of the initial pentacoordinated reagent and occurs via a simultaneous detachment of the vinyl group from the metal and formation of the vinyl-carbonyl bond. The overall thermodynamics and kinetics for the full catalytic cycle have been evaluated and have shown that the Reppe carbonylation of acetylene is a thermodynamically favored and kinetically easy process.