Advisor(s)
Abstract(s)
p-tert-Butylhexahomotrioxacalix[3]arene tri(adamantyl)ketone (1b) was synthesized for the first time. Compound 1b was obtained in a cone conformation in solution at room temperature, as established by NMR spectroscopy (H-1 and C-13). The binding properties of ligand 1b for alkali, alkaline earth, transition, heavy metal and lanthanide cations have been assessed by phase transfer and proton NMR titration experiments. Molecular mechanics and ab initio techniques were also employed to complement the NMR data. The results are compared to those obtained with other closely related homooxacalixarene derivatives. Although triketone 1b is a weak extractant, it shows a strong peak selectivity for Na+ and also some preference for Ag+. Proton NMR titrations indicate the formation of 1:1 complexes between 1b and the cations Studied, and also that they should be located inside the cavity defined by the phenoxy and carbonyl oxygen atoms. Although the molecular mechanics results show little correlation with the NMR data, a good agreement was obtained with the ab initio models. (C) 2008 Elsevier Ltd. All rights reserved.
Description
Keywords
Chemistry, Organic
Pedagogical Context
Citation
TETRAHEDRON. - Vol. 65, n. 2 (2009), p. 496-503
Publisher
PERGAMON-ELSEVIER SCIENCE LTD