Electronic Effects of Bidentate P,N-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 P,N-ligands. To further develop these P,N-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 P,N-ligands were synthesized. The ligand exchange equilibrium and reductive elimination were then characterized using an Au(III)-mediated S-arylation reaction. The results detailed herein provide new fundamental insights in Au(I)/Au(III) ligand design.