Advisor(s)
Abstract(s)
The binding properties of tetra(2-pyridylmethoxy) (2) derived from p-tert-butyldihomooxacalix[4]arene, in the cone conformation, towards alkali, alkaline earth, transition (Mn2+, Fe2+, Co2+, Ni2+, Cu2+ and Zn2+) and heavy (Ag+, Cd2+, Hg2+ and Pb2+) metal cations have been assessed by extraction studies of metal picrates from water into dichloromethane and stability constant measurements in methanol and acetonitrile. Results concerning the calorimetric study of K+, Ba2+, Cu2+ and Ag+ complexes in acetonitrile are presented. The affinity of 2 for some cations (K+, Ag+, Zn2+, Hg2+ and Pb2+) has also been investigated by proton NMR spectrometry. The analogous derivative (3) of p-tert-butylcalix[ 4] arene was also studied, and the results of both compounds are compared. Towards the hard alkali and alkaline earth metal cations ligands 2 and 3 display a low efficiency of extraction. The complexation levels are also low in methanol becoming, however, much higher in acetonitrile. The highest stability is found for Ca2+ with ligand 2 in this solvent. Both ligands show a very high affinity for the soft heavy metal ions with preference for Ag+, but other ions such as Hg2+, Pb2+ and Cu2+ are also well bound. Proton NMR titrations confirm the formation of 1 : 1 complexes between 2 and all the cations studied, also indicating that they should be located inside the cavity defined by the phenoxy oxygen and the pyridyl nitrogen atoms.
Description
Keywords
Chemistry, Multidisciplinary
Pedagogical Context
Citation
NEW JOURNAL OF CHEMISTRY. - Vol. 30, n. 11 (2006), p. 1655-1661
Publisher
ROYAL SOC CHEMISTRY