X-ray diffraction study of benzothiacrown compounds and their complexes with heavy metal cationsстатья

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

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[1] X-ray diffraction study of benzothiacrown compounds and their complexes with heavy metal cations / L. G. Kuz'mina, A. I. Vedernikov, S. N. Dmitrieva et al. // Russian Chemical Bulletin. — 2007. — Vol. 56, no. 5. — P. 1003–1012. The structures of a series of substituted benzothiacrown compounds containing the dithia-15-crown-5, dithia-18-crown-6, or monothia-15-crown-5 fragment and their complexes with Ag+ and Pb2(+) ions were studied by X-ray diffraction. In free benzothiacrown compounds, the sulfur atoms are preferably located outside the macrocyclic cavity, and their lone electron pairs (LEPs) point away from the center of the macrocycle, which is unfavorable for the formation of inclusion complexes. Flexible macrocyclic fragments can change their conformations in accord with the coordination requirements of heavy metal cations. As a result, benzothiacrown compounds involved in complexes adopt a crown conformation, in which LEPs of all hetero-atoms point toward the cation. The sulfur atoms are involved in coordination of Ag+ to a greater degree than the oxygen atoms due to high affinity of soft sulfur atoms for silver cations. On the contrary, the sulfur and oxygen atoms are involved to approximately the same degree in coordination of Pb2(+) ions. [ DOI ]

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