DFT study on the mechanisms of α‐C cross coupling of π‐bonds catalyzed by iron complexes

Abstract

AbstractThe mechanisms of α‐C cross coupling of π‐bonds catalyzed by iron complexes have been investigated using density functional theory (DFT) calculations with the B3LYP‐D3BJ in solvation model density (SMD) (dichloromethane). The results show that the overall catalytic cycle includes the deprotonation of α‐position of alkynes, electrophilic functionalization, protonation and BF3 departure, alkynes exchange, and catalyst regeneration. The deprotonation step of α‐position of alkynes is the rate‐determining step in the whole catalytic cycle where the energy barrier ΔGsol in dichloromethane solution is 11.6 kcal/mol. Our results also show that the product is in a racemic form, which keeps consistent with the experimental results.