Selection of metal ions by geometric isomers of a polyamine macrocycle with pendant donors

Abstract

<p>The <i>syn</i> and <i>anti</i> isomers of 6,13-dimethyl-1,4,8,11-tetraazacyclotetradecane-6,13-diamine (L¹ and L² respectively) have distinctly different shapes for binding metal ions. This is reflected in part in the stability constants for complexation (log <i>K</i>, 25°C, 1:1 complex), which have been determined for the d¹⁰ metal ions Zn²⁺(<i>syn</i>, 16.1; <i>anti</i>, 14.9), Cd²⁺(<i>syn</i>, 12.1; <i>anti</i>, 10.6), Hg²⁺(<i>syn</i>, 12.2; <i>anti</i>, 10.5), and Pb²⁺(<i>syn</i>, 11.8; <i>anti</i>, 10.8), none of which involves ligand-field stabilization contributions to the stability of complexes. The <i>syn</i> isomer, with its sterically undemanding 'nest' shape, displays higher <i>K</i> values than the <i>anti</i> isomer irrespective of metal ion size. Selection of the small zinc(II) ion compared to the larger cadmium(II) ion by both isomers is significant (Δ log <i>K syn</i> 4.0, <i>anti</i> 4.6). The <i>syn</i> isomer accommodates the large lead(II) ion, the [PbL¹(H₂O)][ClO₄]₂ complex crystallizing in the monoclinic <i>P</i>2₁/c space group, <i>Z</i>= 4, <i>a</i>= 8.774(3), <i>b</i>= 17.794(6), <i>c</i>= 15.738(5)Å, β= 109.67(3)°. The lead(II) ion is co–ordinated by all six amines [Pb–N range 2.505(5)–2.809(7)Å], the water molecule [Pb–O 3.098(6)Å] and weakly chelated by a perchlorate ion [Pb–O 3.24(1), 3.298(9)Å]. By contrast, the slightly smaller mercury(II) ion is not accommodated in the cavity of the <i>anti</i> isomer, the isolated complex [(H₂L²)(HgCl₃)₂][L²(HgCl₂)₂]·2H₂O crystallizing in the triclinic <i>P1</i> space group, <i>Z</i>= 1, <i>a</i>= 14.321(4), <i>b</i>= 10.317(2), <i>c</i>= 8.246(2)Å, α= 95.19(2), β= 96.24(2), γ= 97.68(2)°. Two separate molecular units co-exist in equal amounts in the structure, the first with mercury(II) ions bound to each pendant amine in a unidentate manner, whereas the second has two mercury ions chelated at opposite sides of the macrocycle to, in each case, the pendant amine and one secondary amine. In each unit, chloride ions complete the tetrahedral environment for the metal ion, with variable Hg–N [range 2.279(7)–2.364(7)Å] and Hg–Cl [range 2.370(3)–2.535(2)Å] distances.</p>