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Self-Assembly of Dithiolene-based Coordination Polymers of Mercury(II): Dithioether versus Thiocarbonyl Bonding

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Summary.

The reactions of 4,5-bis(methylthio)-1,3-dithiole-2-thione (L) with mercury(II) halides allowed the isolation and structural characterization of three novel coordination polymers, [HgX2L] n (X = I, 1; X = Br, 2; X = Cl, 3). In all cases, the complexation of L on HgX2 occurs via the thiocarbonyl function. The strength of this Hg–S bond decreases from X = I to X = Cl, as indicated by the increasing Hg–S bond distances (2.583(4) 1; 2.668(4) 2; 2.815(5) Å 3). The 1D polymeric structures result from bridging halide interactions and a combination of π–π and S···S interactions between the sulfur rich ligands. The coordination around the Hg center is distorted tetrahedral in 1, whereas the geometry around the mercury in 3 is better described as distorted square pyramidal. In addition, weak interchain interactions are observed in the crystalline state. The preference of HgI2 for thiocarbonyl bonding instead of a chelating dithioether bonding was also studied by means of ab initio calculations.

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Authors and Affiliations

  1. Laboratoire de Chimie des Matériaux et Interfaces, Faculté des Sciences et Techniques, University of Franche-Comté, 25030, Besançon, France

    Aurélien Hameau, Fabrice Guyon & Michael Knorr

  2. Laboratoire de Microanalyses Nucléaires, UMR CEA E4, Faculté des Sciences et Techniques, University of Franche-Comté, Besançon, France

    Mironel Enescu

  3. Institut für Anorganische Chemie der Universität Würzburg, D-97074, Würzburg, Germany

    Carsten Strohmann

Authors
  1. Aurélien Hameau
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  2. Fabrice Guyon
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  3. Michael Knorr
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  4. Mironel Enescu
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  5. Carsten Strohmann
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Correspondence to Michael Knorr.

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Hameau, A., Guyon, F., Knorr, M. et al. Self-Assembly of Dithiolene-based Coordination Polymers of Mercury(II): Dithioether versus Thiocarbonyl Bonding. Monatsh. Chem. 137, 545–555 (2006). https://doi.org/10.1007/s00706-006-0449-5

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  • DOI: https://doi.org/10.1007/s00706-006-0449-5

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