抄録
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.
| 元の言語 | 英語 |
|---|---|
| ページ（範囲） | 4849-4852 |
| ページ数 | 4 |
| ジャーナル | Chemical Communications |
| 巻 | 53 |
| 発行部数 | 35 |
| DOI | |
| 出版物ステータス | 出版済み - 1 1 2017 |
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All Science Journal Classification (ASJC) codes
- Catalysis
- Electronic, Optical and Magnetic Materials
- Ceramics and Composites
- Chemistry(all)
- Surfaces, Coatings and Films
- Metals and Alloys
- Materials Chemistry
これを引用
Catalytic C-H amination driven by intramolecular ligand-to-nitrene one-electron transfer through a rhodium(III) centre. / Fujita, Daiki; Sugimoto, Hideki; Shiota, Yoshihito; Morimoto, Yuma; Yoshizawa, Kazunari; Itoh, Shinobu.
：: Chemical Communications, 巻 53, 番号 35, 01.01.2017, p. 4849-4852.研究成果: ジャーナルへの寄稿 › 記事
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TY - JOUR
T1 - Catalytic C-H amination driven by intramolecular ligand-to-nitrene one-electron transfer through a rhodium(III) centre
AU - Fujita, Daiki
AU - Sugimoto, Hideki
AU - Shiota, Yoshihito
AU - Morimoto, Yuma
AU - Yoshizawa, Kazunari
AU - Itoh, Shinobu
PY - 2017/1/1
Y1 - 2017/1/1
N2 - 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.
AB - 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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U2 - 10.1039/c7cc01840a
DO - 10.1039/c7cc01840a
M3 - Article
VL - 53
SP - 4849
EP - 4852
JO - Chemical Communications
JF - Chemical Communications
SN - 1359-7345
IS - 35
ER -