Cu2+ recognition by N,N′-benzylated bis(amino amides)

Abstract

Two new C₂-symmetric N,N′-benzylated bis(amino amides) have been synthesised and their interaction with different transition metals studied using a variety of techniques including UV-Vis and CD spectroscopy or ESI-MS. The determination of the corresponding stability constants with Cu²⁺ has been possible, in H₂O/CH₃CN 7/3 v/v, for one of these ligands (4) using potentiometric titrations. The results obtained reveal that N-benzylation affords significant changes to their properties and is accompanied by an appreciable decrease in the corresponding complexation stability constants. However, this, along with the low kinetics associated to Ni²⁺, facilitates the recognition of Cu²⁺ by 4 that can be followed by the naked-eye up to the submillimolar range. Very interestingly, the chiral nature of this ligand provides an intense and well defined CD curve for the corresponding Cu²⁺ complex, very sensitive to the coordination geometry, facilitating the analysis of this interaction even at the μM range. The formation by both ligands (3 and 4) of square planar complexes with Cu²⁺ and Ni²⁺ displaying a 1 : 1 stoichiometry was confirmed by their X-ray crystal structures.