Heterometallic Ln/Hg compounds with fluorinated thiolate ligands |
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Authors: | Banerjee Santanu Emge Thomas J Brennan John G |
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Institution: | Department of Chemistry and Chemical Biology, Rutgers, the State University of New Jersey, 610 Taylor Road, Piscataway, New Jersey 08854-8087, USA. |
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Abstract: | The early lanthanide benzenefluorothiolates (Ln(SC(6)F(5))(3); Ln = La, Ce, Pr, Nd, Sm, Gd) react with Hg(SC(6)F(5))(2) in DME to form ionic heterometallic compounds with Ln cations and Hg anions. X-ray diffraction analyses of all compounds reveal an isostructural series with the general formula (DME)(3)Ln(SC(6)F(5))(2)](2)Hg(2)(SC(6)F(5))(6)]. In the structures, a fluorothiolate ligand has been extracted from the Ln coordination sphere that is saturated with three neutral DME donor ligands and a dative interaction between one ortho fluorine and the Ln. Distances between Ln and F do not vary simply with Ln ionic radius. There are two Ln cations with charge balanced by a Hg(2)(SC(6)F(5))(6) dianion composed of two distinctly nonideal Hg(II) tetrahedra, all connected through a series of pi-pi interactions that link cations with anions in a one-dimensional array and anions to anions in a more complex 2D network. |
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