| Title | One-pot, template syntheses of a new class of metallomacrocycles with a tetraoxime cyclic skeleton. | | Author(s) | Tashiro S, Minoda A, Yamada M, Shionoya M | | Institution | Department of Chemistry, Graduate School of Science, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033, Japan. | | Source | Inorg Chem 2009 Nov 2; 48(21):10093-101. | | Abstract | Most common macrocycles such as crown ethers, porphyrins, and macrocyclic polyamines show versatile, excellent functions in a variety of research fields such as coordination chemistry, supramolecular chemistry, analytical chemistry, and material sciences. Thus, the rational design of a new class of readily synthesized macrocyclic metal ligands is a key to the development of a new category of functionalized macrocyclic metal complexes. Herein, we report one-pot, template syntheses of a new class of metallomacrocycles with a 16-membered tetraoxime cyclic skeleton from a dioxime in the presence of a template transition-metal ion such as Fe(2+), Ni(2+), Cu(2+), Co(2+), or Ag(+). These metal ions can be easily removed from the mononuclear metallomacrocycles, and, for example, the metal-free tetraoxime ligand was obtained in 90% yield when Fe(2+) was used as the template. It would appear that this one-pot, metal-template cyclization efficiently proceeds through continual metal-mediated oxime exchange reactions. Interestingly, Pd(2+), which does not afford any cyclized products, formed a 1:1 complex with the macrocyclic ligand. The molecular structures of the metal-free ligand, its 1:1 metal complexes with Fe(2+), Ni(2+), Cu(2+), Pd(2+), and Ag(+), and a dinuclear complex with Ag(+) were fully determined by single-crystal X-ray analyses. UV-visible absorption spectra and cyclic voltammetry measurements of these complexes are also reported. | | Language | eng | | Pub Type(s) | Journal Article
| | PubMed ID | 19852519 |
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