期刊
CHEMICAL COMMUNICATIONS
卷 53, 期 35, 页码 4849-4852出版社
ROYAL SOC CHEMISTRY
DOI: 10.1039/c7cc01840a
关键词
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资金
- JSPS KAKENHI [JP24109014, 23109015]
- CREST, JST [JPMJCR16P1, JPMJCR15P5]
- [2408]
- Grants-in-Aid for Scientific Research [24109015, 16K05725, 17H03117, 16K17878] Funding Source: KAKEN
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.
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