Aryl C-H Amination by Diruthenium Nitrides in the Solid State and in Solution at Room Temperature: Experimental and Computational Study of the Reaction Mechanism

摘要

Diruthenium azido complexes Ru-2(DPhF)-4N-3 (1a, DPhF = N,N'-diphenylformamidinate) and Ru-2(D(3,5-Cl-2)PhF)-4N-3 (1b, D(3,5-Cl-2)PhF = N,N'-bis(3,5-dichloro-phenyl)formamidinate) have been investigated by thermo-lytic and photolytic experiments to investigate the chemical reactivity of the corresponding diruthenium nitride species. Thermolysis of lb at ~100 ℃ leads to the expulsion of N-2 and isolation of Ru-2(D(3,5-Cl-2)PhF)3NH(C-13H-6N-2Cl-4) (3b), in which a nitrogen atom has been inserted into one of the proximal aryl C-H bonds of a D(3,5-Cl-2)PhF ligand.