Synthesis and characterization of nickel(II) and copper(II) complexes of some large-ring macrocycles derived from diethylenetriamine

Abstract

Diethylenetriamine condenses with carbon tetrachloride, tetrachloroethylene, 1,1,2,2-tetrachloroethane, chloroform and dichloromethane in the presence of nickel(II) ions to produce macrocyclic hexaaza ligands, 1,4.7,9,12,15-hexaaza-8,8,16,16,-tetrachlorocyclohexadecane (HTCH), 1,4,7,10,13,16-hexaaza-8,9,17,18-tetrachlorocyclooctadeca-8,17-diene (HTOD), 1,4,7,10,13,16-hexaaza-8,9,17,18-tetrachlorocyclooctadecane (HTCO), 8,16-dichloro-1,4,7,9,12,15-hexaazacyclohexadecane (DHCH) and 1,4,7,9,12,15-hexaazacyclohexadecane (HACH), respectively. But, the template condensation of diethlenetriamine and chloroform in presence of copper(II) ions yields a cage-macrocycle, 2,5,8,10,13,16,17,20,23-nonaazabicyclo[7.7.7]tricosane (NACT). A blue condensed product of diethylenetriamine, dichloromethane and copper(II) ion could not be crystallized from the reaction mixture. The isolated complexes [Ni 2 (HTCH)(H 2 O) 6 ]Cl 4 .7H 2 O, [Ni 2 (HTOD)(H 2 O) 6 ]Cl 4 , [Ni 2 (HTCO)(H 2 O) 6 ]Cl 4 , [Ni 2 (DHCH)(H 2 O) 6 ]Cl 4 .13H 2 O, [Ni 2 (HACH)-(H 2 O) 6 ]Cl 4 .10H 2 O and [Cu 3 (NACT)(H 2 O) 3 ]Cl 6 , and the metal-free ligand NACT.9HCl have been characterized by elemental analyses, conductivity measurements, melting point and spectroscopic studies.