Abstract
The complexation properties of three related macrocycles derived from 4,13-diaza-18-crown-6 toward lead(II) are reported. The flexible macrocycle N,N‘-bis(2-aminobenzyl)-4,13-diaza-18-crown-6 (L2) forms stable complexes with this metal ion in the presence of different counterions (perchlorate and thiocyanate). The X-ray crystal structure of [PbL2](SCN)2 indicates that, in the solid state, the lead(II) ion is eight-coordinated and fits quite well into the crown hole favoring an anti arrangement of the organic receptor, which generates a very infrequent cubic coordination polyhedron around the Pb(II) ion. In solution both complexes are fluxional and the nature of the counterion seems to affect the dynamic behavior. Ligand L3, N,N‘-bis[(2-salicylaldimino)benzyl]-4,13-diaza-18-crown-6, derives from L2 by condensation of salicylaldehyde with the amine group of each side arm. It can be deprotonated to yield cationic complexes of formula [Pb(L3-H)]+ where the metal ion lies asymmetrically on the cavity of the li...
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