Theoretical Investigation on The Reaction Mechanism of 2-methyl-1, 3-cis-butadiene with benzaldehyde Catalyzed by Rh(Ⅰ)

The reaction mechanism of 2-methyl-1, 3-cis-butadiene with benzaldehyde catalyzed by Rh(Ⅰ) has been calculated by DFT, The LanL2DZ basis set has been adopted for Rh. For the other atoms, the 6-31+G^* basis set has been used. In this paper, all the intermediates and transition states have been fully optimized to obtain their molecular geometries and electronic structures. Ground or transition state properties have been established by full-frequency calculations. The energies given below have been corrected for zero point vibrational energy (ZPVE). To further insight into the nature of bonding interaction, AIM analysis has been performed by using AIM2000. The analyses of the charge distribution and charge-transfer processes have been carried out with the NBO theory. Feasible reaction pathways were investigated, which are IA : Re→IMA1→TSA1→IMA2→IMA3→TSA2→IMA4→IMA5→TSA3→IMA6→PA and IB: Re→IMB1→TSB1→IMB2→IMB3→TSB2→IMB4→IMB5T→SB3→IMB6→PB. Computation results indicate that reaction pathway IB is the main pathway, the activation energy of which is smaller, which is in good agreement with experimental results. (authors)