Salt-Enhanced Oxidative Addition of Iodobenzene to Pd: an Inter-play Between Cation, Anion and Pd-Pd Cooperative Effects

Halide salts facilitate the oxidative addition of organic halides to Pd(0). This phenomenon originates from a combina-tion of anionic, cationic and Pd-Pd cooperative effects. Exhaustive computational exploration at the DFT level of the com-plexes obtained from [Pd0(PPh3)2] and a salt (NMe4Cl or LiCl) showed that chlorides promote phosphine release, leading to a mixture of mononuclear and dinuclear Pd(0) complexes. Anionic Pd(0) dinuclear complexes exhibit a cooperativity between Pd(0) centers which favors the oxidative addition of iodobenzene. The higher activity of Pd(0) dimers toward oxidative addition rationalizes the previously reported kinetic laws. In the presence of Li+, the oxidative addition to mon-onuclear [Pd0L(Li2Cl2)] is estimated barrierless. LiCl coordination polarizes Pd(0), enlarging both the electrophilicity and the nucleophilicity of the complex, which promotes both coordination of the substrate and the subsequent insertion into the C-I bond. These conclusions are paving the way to the rational use of salt effect in catalysis for the activation of more challenging bonds.