Iodide-enhanced palladium catalysis via formation of iodide-bridged binuclear palladium complex

The prevalence of metalloenzymes with multinuclear metal complexes in their active sites inspires chemists’ interest in the development of multinuclear catalysts. Studies in this area commonly focus on binuclear catalysts containing either metal-metal bond or electronically discrete, conformationally advantageous metal centres connected by multidentate ligands, while in many multinuclear metalloenzymes the metal centres are bridged through μ2-ligands without a metal-metal bond. We report herein a μ2-iodide-bridged binuclear palladium catalyst which accelerates the C-H nitrosation/annulation reaction and significantly enhances its yield compared with palladium acetate catalyst. The superior activity of this binuclear palladium catalyst is attributed to the trans effect-relay through the iodide bridge from one palladium sphere to the other palladium sphere, which facilitates dissociation of the stable six-membered chelating ring in palladium intermediate and accelerates the catalytic cycle. Such a trans effect-relay represents a bimetallic cooperation mode and may open an avenue to design and develop multinuclear catalysts.