Journal
POLYHEDRON
Volume 26, Issue 14, Pages 3763-3773Publisher
PERGAMON-ELSEVIER SCIENCE LTD
DOI: 10.1016/j.poly.2007.04.037
Keywords
2-ethanethiol-cyclen derivative; protonation constants; stability constants; protonation sequence; C-13 NMR titration; EPR
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The compound 2-[1,4,7, 10-tetraazacyclododecan-1-yl]-ethanethiol (L2) has been synthesized and characterized by multinuclear NMR spectroscopy and mass spectrometry. Its thiol-protected precursor L1 has also been isolated and characterized, including by X-ray structural analysis. The protonation constants of L2 were determined by potentiometric methods at 25.0 degrees C and 0.10 mol dm(-3) KNO3 ionic strength. 13 C NMR studies and 2D NMR spectra recorded at different pD values have been used to analyse its protonation scheme. Stability constants of L2 with Cu2+, Zn2+ and Cd2+ were also determined by potentiometry, and the Zn(II) and Cu(II) complexes were studied in solution by NMR, UV-Vis, and EPR spectroscopies. The pM values (pH 7.4) calculated for the metal complexes of L2 are higher than the corresponding values found for cyclen and cyclam, but the selectivity of L2 for Cu2+ is low. (c) 2007 Elsevier Ltd. All rights reserved.
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