Department of Chemistry, University of Wisconsin-Madison, 1101 University Avenue, Madison, Wisconsin 53706, USA.
J Am Chem Soc. 2010 Sep 8;132(35):12228-30. doi: 10.1021/ja1062955.
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.
末端叠氮基 Ru(2)(D(3,5-Cl(2))PhF)(3)N(3)（3，D(3,5-Cl(2))PhF = N,N'-双(3,5-二氯苯基)甲脒基）的热解可干净地生成 Ru(2)[(D(3,5-Cl(2))PhF)(3)(D(3,5-Cl(2)-2-NH)PhF)]（4），据推测，这是由于氮化物 N 原子插入配体芳基 C-H 键中所致。这种机制得到了差示扫描量热法和热重分析结果的支持，这些结果表明两步反应放热为-215 kJ mol(-1)，与密度泛函理论计算的结果一致。这是首例末端氮化物对芳族 C-H 键的亲电插入的实例。
