15-Hydroxybenzomonothia-15-crown-5 with the sulfur atom linked with the benzene ring and the derived sulfoxide: synthesis, structure, and complexation with the metal cationsстатья

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Дата последнего поиска статьи во внешних источниках: 18 июля 2013 г.

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[1] 15-hydroxybenzomonothia-15-crown-5 with the sulfur atom linked with the benzene ring and the derived sulfoxide: synthesis, structure, and complexation with the metal cations / A. I. Vedernikov, L. G. Kuz'mina, Y. A. Strelenko et al. // Russian Chemical Bulletin. — 2010. — Vol. 59, no. 5. — P. 927–940. Novel 15-hydroxybenzomonothia-15-crown-5 containing the sulfur atom linked with the benzene ring and its S-oxide were synthesized. The stability constants for the complexes of the obtained benzocrown ethers and a reference 15-hydroxybenzo-15-crown-5 with Na, Ca, Ag(I), Cd, Hg(II), and Pb(II) perchlorates were determined by (1)H NMR titration. In MeCN-d(3), the benzothiacrown ether demonstrates a high selectivity towards the thio- and oxothiophilic Hg(2+) (logK (1) = 7.1) and Pb(2+) ions (logK (1) = 7.4). In MeCN-d(3)-D(2)O mixtures, the stabilities of the most of complexes decrease sharply due to competitive hydration of the metal cations except for the "soft" Ag(+) and Hg(2+) ions having low affinity for the "hard" oxygen atoms and, on the contrary, very high affinity for the "soft" S(II) atoms. This results in the change in selectivity of complexation: at the water content in solution of 20%, the benzothiacrown ether binds preferably the Hg(2+) (logK (1) = 5.0) and Ag(+) ions (logK (1) = 2.7). In MeCN-d(3), the benzothiacrown-derived sulfoxide is a weak and non-selective complexing agent towards all the metal cations under study; the reference 15-hydroxybenzo-15-crown-5 forms more stable complexes with the oxophilic sodium, calcium, and lead(ii) cations. The conformational features of the benzocrown ethers and their metal complexes established by NMR spectroscopy and X-ray diffraction are discussed. The found characteristics of the complexing ability of benzomonothia-15-crown-5 where the sulfur atom is in conjugation with the benzene ring reveal that the macrocyclic ligands with such a structure are promising as high-selective and efficient complexing agents for the "soft" mercury(ii) and silver(i) cations in acetonitrile-water mixtures. [ DOI ]

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