AbstractThe potentiometric study of the complexation of Cu2+with 1,4,7‐triazacyclononane (1), 1,4,8‐triazacyclodecane (2) 1,5,9‐triazacyclododecane (3) has shown that CuL, CuL2and (CuLOH)2are the main species present in solution. Their stabilities (Table 1) and their absorption spectra (Table 2) indicate facial coordination of the cyclic triamines in a distorted octahedral geometry.The formation and dissociation kinetics have been measured by stopped‐flow techniques. The formation in acetate buffer can be described by the reaction of Cu2+and CuAcO+with the monoprotonated species of the ligand. The bimolecular rate constants for these complexations (Table 3) decrease when the ring size increases. In contrast the dissociation induced by acid is only little affected by the ring size. Thus for these complexes the rate of formation and not that of the dissociation determines the overall st