Mechanistic Exploration of the Transmetalation and Reductive Elimination Events Involving PdIV–Abnormal NHC Complexes in Suzuki–Miyaura Coupling Reactions: A DFT Study

Abstract A comprehensive DFT (M06‐L‐D3(SMD)/BS2//M06‐L/BS1 level) investigation has been carried out to explore in detail the mechanism of the transmetalation and reductive elimination reactions of abnormal N‐heterocyclic carbene (aNHC) palladium(IV) complexes within the framework of Suzuki–Miyaura cross‐coupling reactions. Emphasis was placed on the role of base and the effect of countercations on the critical transmetalation and reductive elimination events involving palladium(IV) complexes. Of the two competing roles of the base, the route involving boronate formation followed by halide exchange prevails over that of direct halide exchange for the intermediates [PdIV(aNHC)(OMe)2Cl]−Na+ (pathway A), [PdIV(aNHC)(OMe)(Cl)2]−Na+ (pathway B), and [PdIV(aNHC)Cl3]−Na+ (pathway C) emanating from the oxidative addition reaction. The results of the calculations are in accordance with our previous theoretical findings of favorable energetics for palladium intermediates incorporating two coordinated methoxy groups. The negative role played by the countercation in the transmetalation step is mainly due to the overstabilization of the pre‐transmetalation intermediate, which is in line with experimental kinetic results. The anionic complexes exhibit greater affinity for the transmetalation and reductive elimination reactions than the neutral variants.