Computational Modelling of Selectivity in Cobalt‐Catalyzed Propene Hydroformylation

Abstract A mechanistic model for the cobalt‐catalyzed hydroformylation of propene, based on density functional theory and coupled cluster electronic structure calculations and transition state theory, is proposed to explain the experimentally observed reactivity and selectivity. The electronic structure calculations provide very accurate energies, which are used with transition state theory to compute rate constants; the kinetics of the network of coupled reactions are then modelled numerically for this organometallic reaction. The model accounts well for the dependence of rate on the concentrations of catalysts and reagents, and also on the temperature, and the agreement with experiment is improved still further upon making small adjustments to the ab initio calculated free energy values. The calculations provide detailed kinetic insight into the mechanism of hydroformylation and the role of various elementary steps in defining reactivity and selectivity.