Full kinetic analysis of a rhodium-catalyzed hydroformylation: beyond the rate-limiting step picture

Abstract

A complete dynamic kinetic analysis beyond the steady state approximation of the rhodium-catalyzed hydroformylation with the 6-DPPon ligand is presented. The energy profile was calculated using a CCSD(T):B3LYP scheme. The results are compatible with the experimental trends for this system with regard to the activity, the selectivity and the substrate dependencies. In contrast to the classical understanding of the kinetics, not one rate-limiting step or energetic span governs the catalytic reaction. Conversely, the kinetic analysis shows that several intermediates and transition states control the reaction rate and the selectivity.