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.
Long
Amanda Kae Musch
AK
Department of Chemistry, University of Wisconsin-Madison, 1101 University Avenue, Madison, Wisconsin 53706, USA.
Yu
Renyuan Pony
RP
Timmer
George H
GH
Berry
John F
JF
D000586:Amination; D056831:Coordination Complexes / Q000737:chemistry*; D018360:Crystallography, X-Ray; D008958:Models, Molecular; D056004:Molecular Dynamics Simulation; D017672:Nitrogen Compounds / Q000737:chemistry*; D009942:Organometallic Compounds / Q000737:chemistry*; D012428:Ruthenium / Q000737:chemistry*; D013696:Temperature
D056831:Coordination Complexes; D017672:Nitrogen Compounds; D009942:Organometallic Compounds; D012428:Ruthenium