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.