The pyrimidinethiolate complexes ∞ 3 [Zn(S‐2‐N 2 C 4 H 3 ) 2 ], ∞ 2 [Cd(S‐2‐N 2 C 4 H 3 ) 2 ] and [Hg(S‐2‐N 2 C 4 H 3 ) 2 ] have been prepared by reaction of MCl 2 (M = Zn, Cd, Hg) with 2 equiv. of Me 3 SiS‐2‐N 2 C 4 H 3 in organic solvents, whilst [Cd(S‐2‐N 2 C 4 H 3 ) 2 (tmeda)] was obtained by recrystallisation of ∞ 2 [Cd(S‐2‐N 2 C 4 H 3 ) 2 ] in TMEDA at 40 °C. The structures of the complexes were determined by single‐crystal X‐ray crystallography, which shows that the different metal atoms each have different coordination environments. The zinc atom in ∞ 3 [Zn(S‐2‐N 2 C 4 H 3 ) 2 ] exhibits a tetrahedral coordination with one sulfur and three nitrogen atoms from pyrimidinethiolate ligands, whereas the cadmium atoms in ∞ 2 [Cd(S‐2‐N 2 C 4 H 3 ) 2 ] and [Cd(S‐2‐N 2 C 4 H 3 ) 2 (tmeda)] are six‐coordinate with either three sulfur and three nitrogen atoms or two sulfur and four nitrogen atoms. In contrast, the mercury atoms in [Hg(S‐2‐N 2 C 4 H 3 ) 2 ] display a distorted square‐planar coordination to a pair of chelating – S‐2‐N 2 C 4 H 3 ligands with additional weak Hg–S interactions to adjacent molecules. While known cadmium and zinc pyrimidinethiolate complexes consist of one‐dimensional chains, ∞ 3 [Zn(S‐2‐N 2 C 4 H 3 ) 2 ] and ∞ 2 [Cd(S‐2‐N 2 C 4 H 3 ) 2 ] form either three‐ or two‐dimensional polymeric networks of metal atoms. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)
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Eichhöfer et al. (2005) studied this question.
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