Electronic Effects\nof Bidentate <i>P</i>,<i>N</i>‑Ligands\non the Elementary Steps of Au(I)/Au(III)\nReactions Relevant to Cross-Coupling Chemistry

Oxidant-free Au(I)/Au(III)-catalyzed cross-coupling has\nbeen recently\nenabled by the use of bidentate <i>P</i>,<i>N</i>-ligands. To further develop these <i>P</i>,<i>N</i>-ligands, computational studies were performed to understand their\neffects on the oxidative addition of aryl iodide electrophiles with\nAu(I). Using this mechanistic understanding, six new electron-rich <i>P</i>,<i>N</i>-ligands were synthesized. The ligand\nexchange equilibrium and reductive elimination were then characterized\nby using a Au(III)-mediated <i>S</i>-arylation reaction.\nThe results detailed herein provide new fundamental insights in Au(I)/Au(III)\nligand design.