Density Functional Theory Investigation of the Alkyl–Alkyl Negishi Cross‐Coupling Reaction Catalyzed by N‐Heterocyclic Carbene (NHC)–Pd Complexes

Abstract Why bigger is better : A “steric wall” created by the N ‐(2,6‐diisopropylphenyl) substituent on the bulky NHC ligand IPr (1,3‐bis(2,6‐diisopropylphenyl)imidazol‐2‐ylidene) guides the reactants to and from the Pd center through weak, fleeting (IPr)H–Pd interactions that help the oxidative addition intermediate escape “the anti‐trap”. The alternative “side” approach leads to transmetalation (the rate‐limiting step) for which a novel Pd–Zn interaction was identified. magnified image A novel mechanism is proposed for the Pd–1,3‐(2,6‐diisopropylphenyl)imidazolyl‐2‐ylidene ( 1 ) catalyzed Negishi reaction. DFT computations supported by atoms‐in‐molecules (AIM) analyses of non‐truncated models show that a “steric wall” created by the N ‐substituent on the ligand guides reactants to and from the Pd center. Notably, transmetalation and not oxidative addition is found to be rate‐limiting. Additionally, a key Pd–Zn interaction (≈2.4 Å, ρ b ≈0.0600 au) is identified in the mechanism. This interaction persists beyond reductive elimination and, in combination with the ligand, facilitates reductive elimination by creating a highly sterically crowded environment in the coordination sphere of the Pd center.