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.
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The authors gratefully acknowledge support from the National Science Foundation (CHE-0315954). We also thank Dr. Victor G. Young for his assistance with the single crystal XRD experiments.