Herein we first report the unprecedented synthesis of tetrazene-based cobalt complexes using unusual coupling of amines via dehydrogenation. These cobalt complexes were employed for dehydrogenative coupling reactions to synthesize N-heterocycles (quinoline, and quinazolinone). Based on control experiments and IR identification of intermediates, we proposed a plausible reaction mechanism. Synthesis protocols were utilized for preparative scale synthesis and biologically active molecule (±)-galipinine synthesis.