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Zinc, Cadmium, and Mercury 1,2-Benzenedithiolates with Intramolecular NH···S Hydrogen Bonds

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Chemical Analysis Research Center, National Institute for Agro-Environmental Sciences, Tsukuba, Ibaraki 305-8604, Japan, and Department of Macromolecular Science, Graduate School of Science, Osaka University, Toyonaka, Osaka 560-0043, Japan
* To whom correspondence should be addressed. E-mail: [email protected]
†National Institute for Agro-Environmental Sciences.
‡Osaka University.
Cite this: Inorg. Chem. 2008, 47, 7, 2837–2848
Publication Date (Web):March 11, 2008
Copyright © 2008 American Chemical Society

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    Abstract Image

    Mononuclear Zn, Cd, and Hg 1,2-benzenedithiolates with intramolecular NH···S hydrogen bonds, [MII{1,2-S2-3,6-(RCONH)2C6H2}2]2− (R = CH3, t-Bu; M = Zn, Cd, Hg), were synthesized and characterized by X-ray analysis and spectral measurements. The presence of intramolecular NH···S hydrogen bonds was established by the IR spectra. 199Hg and 113Cd nuclear magnetic resonance showed a stabilized four-thiolate coordinated structure and suggested the influence of the NH···S hydrogen bonds to pπ(Hg)−pπ(S) interactions. The NH stretching bands show that the NH···S hydrogen bonds in Cd and Hg complexes are stronger than those in the corresponding Zn complex. These results are supported by theoretical calculations. The experimental and theoretical results suggested that the NH···S hydrogen bond influences the efficient capture of toxic Cd and Hg ions by metallothioneins.

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    X-ray crystallographic files in CIF format, full optimized geometries and NBO analysis using B3LYP functional and various basis sets (Table S1), the detailed second-order perturbation energy analysis (Table S2), a proposed ligand-dissociation equilibrium of 14 (Figure S1), oxidation potentials (Table S3), and cyclic voltammograms (Figure S2 and S3). This material is available free of charge via the Internet at

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