Electronic Effects of Bidentate ,-Ligands on the Elementary Steps of Au(I)/Au(III) Reactions Relevant to Cross-Coupling Chemistry.

Oxidant-free Au(I)/Au(III)-catalyzed cross-coupling has been recently enabled by the use of bidentate ,-ligands. To further develop these ,-ligands, computational studies were performed to understand their effects on the oxidative addition of aryl iodide electrophiles with Au(I). Using this mechanistic understanding, six new electron-rich ,-ligands were synthesized. The ligand exchange equilibrium and reductive elimination were then characterized by using a Au(III)-mediated -arylation reaction. The results detailed herein provide new fundamental insights in Au(I)/Au(III) ligand design.