A ruthenium bisammine complex was formed in the reaction of primary amines with a ruthenium dibenzyltetraazadiene complex. The ruthenium bisammine complex was a convenient precursor for the synthesis of various Ru(II) complexes containing a sterically demanding cyclopentadienyl ligand through ligand exchange reactions. In addition, ruthenium diaryltetraazadiene complexes and coordinatively unsaturated ruthenium imido complexes were obtained in the reaction with aryl azides. The ruthenium complexes were used to catalyst for the reaction of alkyl azides with primary amines to give N-substituted imines.