The preparations of the pentaazamacrocyclic ligands 1,4,7,10,13-pentaazacyclopentadecane, cpad, 1,4,7,10,13-pentaazacyclohexadecane, ched, 1,4,7,10,14-pentaazacycloheptadecane, chad, 1,4,7,11,14-pentaazacycloheptadecane, chbd, 1,4,7,11,15-pentaazacyclooctadecane, coad, 1,4,8,11,15-pentaazacyclooctadecane, cobd, 1,4,8,12,16-pentaazacyclononadecane, cnad, and 1,5,9,13,17-pentaazacycloeicosane, ceic, as well as the new linear pentaamine N-(3-aminopropyl)-N'-propyl>propane-1,3-diamine, tpah, are described.Copper(II) and nickel(II) complexes of the a bove ligands have been prepared and characterized.The nickel(II) complexes of the smaller macrocycles and the linear pentaamine contain NiII in a tetragonally distorted octahedral environment in the presence of coordinating anions or in aqueous solution but the 2+ and 2+ cations are five-coordinate both in the solid state and in aqueous solution.The copper(II) complexes of the macrocyclic pentaamines appear to be square-pyramidal on the basis of their electronic spectra, whereas the complex 2+ is probably trigonal-bipyramidal.