Heterometallic Ln/Hg Compounds with Fluorinated Thiolate Ligands

The early lanthanide benzenefluorothiolates (Ln(SC6F5)3; Ln = La, Ce, Pr, Nd, Sm, Gd) react with Hg(SC6F5)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)3Ln(SC6F5)2]2[Hg2(SC6F5)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 Hg2(SC6F5)6 dianion composed of two distinctly nonideal Hg(II) tetrahedra, all connected through a series of π−π interactions that link cations with anions in a one-dimensional array and anions to anions in a more complex 2D network.