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Issue 10, 2002
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Macrocyclic ligand design. Structure–function relationships involving the interaction of pyridinyl-containing, mixed oxygen–nitrogen donor macrocycles with cobalt(II), nickel(II), copper(II), zinc(II), cadmium(II), silver(I) and lead(II)

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Abstract

A comparative investigation of the interaction of three dibenzo-substituted, mixed oxygen–nitrogen donor macrocycles with cobalt(II), nickel(II), copper(II), zinc(II), cadmium(II), silver(I) and lead(II) has been carried out. The thermodynamic stabilities of the respective complexes in 95% methanol (I = 0.1; Et4NClO4, 25 °C) have been determined. All ligands form 1 ∶ 1 (metal ∶ ligand) species with the above metal ions. The results are compared with those obtained previously for related mixed-donor (cyclic) systems. Single crystal structures of six metal complexes of these 20-membered ring ligands have been determined by X-ray diffraction. All of the macrocyclic donor sites participate in binding to the metal ion in the copper(II) and cadmium(II) complexes. The copper complex is six-coordinate, while the cadmium complex is eight-coordinate with the addition of a bidentate nitrato ion. A tri-nuclear complex is formed on complexation with silver(I) in which two silver-containing macrocycles are linked by a bridging two-coordinate silver ion. The metal atoms in each of the cobalt(II), nickel(II) and zinc(II) complexes are six-coordinate, however, they are bound to the macrocycle only at the three secondary amine nitrogen sites. The coordination sphere is completed by two nitrato counterions in the zinc(II) complex, and by a nitrato ion and a methanol molecule in each of the cobalt(II) and nickel(II) complexes.

Graphical abstract: Macrocyclic ligand design. Structure–function relationships involving the interaction of pyridinyl-containing, mixed oxygen–nitrogen donor macrocycles with cobalt(ii), nickel(ii), copper(ii), zinc(ii), cadmium(ii), silver(i) and lead(ii)

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Publication details

The article was received on 01 Feb 2002, accepted on 19 Mar 2002 and first published on 24 Apr 2002


Article type: Paper
DOI: 10.1039/B201195F
Citation: J. Chem. Soc., Dalton Trans., 2002,0, 2185-2193
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    Macrocyclic ligand design. Structure–function relationships involving the interaction of pyridinyl-containing, mixed oxygen–nitrogen donor macrocycles with cobalt(II), nickel(II), copper(II), zinc(II), cadmium(II), silver(I) and lead(II)

    R. R. Fenton, R. Gauci, P. C. Junk, L. F. Lindoy, R. C. Luckay, G. V. Meehan, J. R. Price, P. Turner and G. Wei, J. Chem. Soc., Dalton Trans., 2002, 0, 2185
    DOI: 10.1039/B201195F

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