Synthesis and Cu(II) coordination of two new hexaamines containing alternated propylenic and ethylenic chains:: Kinetic studies on pH-driven metal ion slippage movements

The synthesis of the open-chain and cyclic polyamines, 1,5,8,12,15,19-hexaazaheptadecane (L1) and 2,6,9,13,16,20-hexaaza[21]-(2,6)pyridinophane (U), are described. The protonation constants and interaction constants with Cu(II) have been determined by potentiometric measurements carried out at 298.1 K in 0.15 mol dm(-3) NaClO4. The values obtained are discussed as a function of the open-chain or cyclic nature of the ligands and compared with analogous polyamines containing different sets of hydrocarbon chains between the nitrogen donors. Kinetic studies on the acid-promoted dissociation of the Cu(II) complexes indicate that the mono and binuclear complexes of L1 decompose with different kinetics, a behavior unprecedented for open-chain polyamines. In contrast, the dissociation of the first metal ion is accelerated in the binuclear complexes of L2 and so, all the mono and binuclear complexes of L2 decompose with the same kinetics. The voltammetric response of Cu(II)-L1 and Cu(II)-L2 complexes has been studied in order to correlate electrochemical and structural data. (c) 2006 Elsevier B.V. All rights reserved.