Copper(II) Complexes with Some Hexaaza Macrocyclic Ligands

Abstract

The template condensation of the chlorocarbons carbon tetrachloride, 1, 1, 2, 2-tctrachloroethylene or 1, 1, 2, 2- tetrachlo-roethane with diethylenetriamine in the presence of copper(II) hydroxide in butanol yields dimetallic copper(II) complexes of the macrocyclic ligands 1, 4, 7, 9, 12, 15-hexaaza-8, 8, 16, 16-tetrachlorocyclohexadecane (HTCH), 1, 4, 7, 10, 13, 16-hexaaza-8, 9, 17, 8-tetrachlorocyclooctadeca-8, 17-diene (HTOD) or l, 4, 7, 10, 13, 16-hexaaza-8, 9, 17, 18-tetrachlorocyclooctadccane (HTCO). respectively. The metal-free ligand hydrochlorides have also been obtained by removing the metal as CuS from the acidic solutions of the corresponding complexes. The formulation of the macrocyclic complexes as [Cu₂(HTCH)(H₂O)₂]Cl₄.8H₂O, [Cu₂(HTOD)(H₂O)₂]Cl₄.H₂O and [Cu₂(HTCO)(H₂O)₂]Cl₄. and the ligands as C₁₀H₂₂N₆Cl₄. 6HCl (HTCH·6HC1), Cl₂H₂₂N₆Cl₄·6HCl (HTOD·6HCl) and C₁₂H₂₆N₆Cl₄·6HCl (HTCO.6HCl) is supported by the elemental analyses, conductivity measurements, molecular weights by mass spectroscopy and infrared spectra.