A density functional theory study of alkyl group migration in RMn(CO)5 complexes

The kinetics of alkyl group migration in RMn(CO)5 complexes ( R=CH3, C2H5 and C3H7) were studied. Isomers of CH3Mn(CO)5 with an agostic structure, an η1 structure, and an η2 structure were found to be local minima on the systemʹs potential energy surface. Transition states for the inter-conversion of these species were also located. The activation free energy for this migration reaction was compared with experimental data and provides insights into the important steps in the overall reaction mechanism.