Catalytic C-H amination driven by intramolecular ligand-to-nitrene one-electron transfer through a rhodium(III) centre
Catalytic C-H amination driven by intramolecular ligand-to-nitrene one-electron transfer through a rhodium(III) centre
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DOI：
10.1039/c7cc01840a
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发表时间：
2017-05-01
影响因子：
4.9
通讯作者：
Itoh, Shinobu
中科院分区：
文献类型：
--
作者：
Fujita, Daiki;Sugimoto, Hideki;Itoh, Shinobu
合成了由一个平面三阴离子配体和两个轴向苯胺配体配位的Werner型六配位铑（III）配合物。三阴离子配体表现为氧化还原活性配体，以在络合物的单电子氧化后形成配体自由基物质。铑（（III））配合物催化C-H胺化的外部底物，如吨与甲苯磺酰叠氮化物作为氮烯源。DFT-计算和动力学氘同位素效应表明，双自由基铑（（III））配合物形成的一个电子转移从氧化还原活性配体的氮烯基团作为一个反应性中间体，以诱导脂肪族C-H活化。
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.