Derivatives of cyclam-1,8-diacetic acid: Synthesis and complexes with divalent transition metal ions

Abstract

1,4,8,11-tetraazacyclotetradecane-1,8-diacetatic acid, H2te2a, and series of its derivative bearing two substituted N-benzyl groups were synthesized and their complexes were studied. Series of CoII and ZnII complexes was prepared in the solid-state and X-ray diffraction analysis showed that the metal ions are hexacoordinated by four nitrogen atoms of the macrocycle and two oxygen atoms of the carboxylate pendants. The two oxygen atoms were in cis and trans mutual position in the CoII and ZnII complexes, respectively. Potentiometric study of CoII, ZnII, CuII and NiII-H2te2a systems showed that the complexes are highly thermodynamically stable and the ligand is selective for CuII ions (logK = 27.5) over the other ions (logK = 21–22). UV-VIS and electrochemical data for the CoII-H2te2a system showed that complexation was rather slow (several hours at pH 4.5, 25 °C) and the complex undergoes slow oxidation with air oxygen.