Mechanism of rhodium‐catalyzed hydroacylation of propylene using formaldehyde: A computational study

Density functional theory was used to study Rh(I)‐catalyzed hydroacylation of propylene and formaldehyde. All the intermediates and the transition states were optimized completely at the B3LYP/6‐311++G(d,p) level (LANL2DZ(d) for Rh, P). Calculation results confirm that Rh(I)‐catalyzed hydroacylation of propylene and formaldehyde is exothermic, and the total released Gibbs free energy is about −33 kJ mol −1 . This hydroacylation have eight possible pathways, and pathways (1), (2), (3), and (4) are the dominant reaction channels. The dominant product predicted theoretically is butyl aldehyde, and it is a linear product, which agrees well with these experiments. © 2009 Wiley Periodicals, Inc. Int J Quantum Chem, 2010