Reactions of an Anionic Gallylene with Azobenzene or Azide Compounds Through C(sp)-H and C(sp)-H Activation.

The activation of inert C-H bonds remains a challenge in current chemistry. Here, we report the excellent reactivity of the anionic gallylene species [LGa:][Na(THF)] (L = [(2,6-PrCH)NC(CH)], ) that allows the selective activation one sp C-H bond of several azobenzene and azide derivatives at ambient temperature, with the transfer of the hydrogen atom to one of the nitrogen atoms. The process leads to the formation of the aryl amido products [LGa-κN,C-PhNN(H)(-R-CH)][Na(solvent)] (, R = H solvent = DME (1,2-Dimethoxyethane); , R = -OMe, solvent = DME; , R = -NMe solvent = THF), [LGa-κN,C-(-CH-CH)NN(H)(-CH-CH)][Na(15-C-5)] () with new Ga-C and Ga-N bonds.