Werner type six-coordinate rhodium(iii) complexes coordinated by a planar trianionic ligand and two axial aniline ligands are synthesised. The trianionic ligand behaves as a redox-active ligand to form a ligand radical species upon one-electron oxidation of the complex. The rhodium(iii) complexes catalyse C-H amination of external substrates such as xanthene with tosylazide as the nitrene source. DFT-calculation and kinetic deuterium isotope effects indicate that a di-radical rhodium(iii) complex formed by one-electron transfer from the redox-active ligand to the nitrene group works as a reactive intermediate to induce aliphatic C-H activation.
All Science Journal Classification (ASJC) codes
- Electronic, Optical and Magnetic Materials
- Ceramics and Composites
- Surfaces, Coatings and Films
- Metals and Alloys
- Materials Chemistry