Non-trivial solution chemistry between amido-pyridylcalixarenes and some metal salts
Colleran, John and Creaven, Bernadette and Donlon, Denise and McGinley, John (2010) Non-trivial solution chemistry between amido-pyridylcalixarenes and some metal salts. Dalton Transactions, 39 . pp. 10928-10936. ISSN 1477-9226
Mercury ion complexation reactions were carried out between 3 and various mercury(II) salts. 1H NMR studies showed that the role of solvent, the anion chosen and the initial reaction conditions were critical and that the formation of a “simple” mercury(II) complex was non-trivial. The mercury(II) ion can cause either (i) the formation of an ion-pair system, which have a characteristic doubling of all signals in the 1H NMR spectrum, (ii) a cleavage reaction to occur resulting in the reformation of the calixarene diester compound 2, but only when the reaction is heated and (iii) “simple” mercury binding to the pyridine rings when the binding studies are carried out using NMR titration techniques. The electrochemistry results, on the same systems, show that the initial reaction involves the removal of the phenoxide protons followed by the resulting catalysis of the mercury species. This proton removal is not observed in the NMR spectra of any of the mercury reactions. It was also found that 3 could bind silver and zinc salts and was not selective for mercury(II) as was previously described.
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