Synthesis and X-ray crystallographic structures of [HGa(NMe2)2]2 and [PhGa(NHNMe2)2]2, and room-temperature conversions of [HGa(NMe2)2]2 to (HGaNH)n and (HGaNMe)n

The reactivity of bis(dimethylamido) complexes of phenyl- and hydridogallium with ammonia, dimethylamine and 1,1-dimethylhydrazine is described. Synthesis of the starting gallium hydride, [HGa(NMe2)2]2, was achieved in nearly quantitative yield from the reaction of HGaCl2(quinuclidine) with LiNMe2. In neat ammonia or methylamine at room temperature both dimethylamido ligands in [HGa(NMe2)2]2 were substituted by a single equivalent of NH3 or MeNH2 to produce amorphous (HGaNH)n or (HGaNMe)n, respectively. In contrast, the reaction of [PhGa(NMe2)2]2 with neat Me2NNH2, at room temperature consumed two equivalents of the substituted hydrazine to form [PhGa(NHNMe2)2]2 in a 73% yield. Single crystal X-ray crystallographic analyses of [HGa(NMe2)2]2 and [PhGa(NHNMe2)2]2 establish that in the solid state both compounds adopt a cyclic Ga–N–Ga–N structure with a crystallographic center of symmetry located at the center of the ring.