Density Functional Theory olefin insertion

In the case that the olefin insertion into a Rh-H bond is irreversible, the enantio-face of a prochiral olefin is discriminated during this step. Thus, the structure of the Rh complex at the transition state becomes important. Here, we introduce an example of a theoretical approach most recently reported by Herrmaim and his coworkers [77,78]. The two structures shown in Fig. 2 as TSI and TSII illustrate the possible transition states of olefin insertion into RhH(CO) (R,S)-BINAPHOS. Density functional theory calculations on model rhodium complexes bearing... 

Lewis bases also accelerate the PKR by supposedly acting as weak ligands to promote the dissociation of CO and to stabilize intermediates. However, density functional theory (DFT) calculations described by Gimbert demonstrate no acceleration for the loss of CO in the presence of a Lewis base. Instead, the calculations suggest that the Lewis base stabilizes the cobaltacycle 1-4. This stabilization effectively makes the olefin insertion irreversible. Dimethylsufoxide, amines such as... 

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