Macrocyclic ligand design: Structure-function relationships involving the interaction of pyridinyl-containing, mixed oxygen-nitrogen donor macrocycles with cobalt(II), nickel(II), zinc(II), cadmium(II), silver(I) and lead(II)
Journal Publication ResearchOnline@JCUAbstract
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.
Journal
Dalton Transactions
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Volume
2002
ISBN/ISSN
1477-9234
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Pages Count
9
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Publisher
Royal Society of Chemistry
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Publisher Location
Cambridge, United Kingdom
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DOI
10.1039/b201195f