Aryl C-H Bond Amination by an Electrophilic Diruthenium Nitride

Thermolysis of the terminal azido Ru-2(D(3,5-Cl-2)PhF)(3)N-3 (3, D(3,5-Cl-2)PhF = N,N'-bis(3,5-dichlorophenyl) formamidinate) cleanly produces Ru-2[(D(3,5-Cl-2)PhF)(3)(D(3,5-Cl-2-2-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.