Aryl C−H Bond Amination by an Electrophilic Diruthenium Nitride

Thermolysis of the terminal azido Ru2(D(3,5-Cl2)PhF)3N3 (3, D(3,5-Cl2)PhF = N,N′-bis(3,5-dichlorophenyl) formamidinate) cleanly produces Ru2[(D(3,5-Cl2)PhF)3(D(3,5-Cl2-2-NH)PhF)] (4), which is proposed to result from insertion of a nitrido N atom into a ligand aryl C−H bond. This mechanism is supported by differential scanning calorimetry and thermogravimetric analysis results, which show the two-step reaction to be exothermic by −215 kJ mol−1, in agreement with results from density functional theory calculations. This is the first example of electrophilic insertion of a terminal nitride into an aromatic C−H bond.对端基叠氮配合物Ru₂(D(3,5-Cl₂)PhF)₃N₃（其中D(3,5-Cl₂)PhF为N,N'-二(3,5-二氯苯基)甲脒基）进行热解，可干净地生成Ru₂[(D(3,5-Cl₂)PhF)₃(D(3,5-Cl₂-2-NH)PhF)]（产物4）。该产物被认为是由端基氮宾（nitrido）的氮原子插入配体芳基C−H键而形成的。差示扫描量热法（differential scanning calorimetry）与热重分析结果为该反应机理提供了支撑：两步反应的焓变为−215 kJ·mol⁻¹，属于放热过程，这与密度泛函理论（density functional theory）的计算结果一致。这是首例端基氮化物向芳基C−H键发生亲电插入的案例。