Metathesis reaction of the dithioether complex cis‐[PtCl2{(PhSCH2)2SiPh2}] (2a) with NaBr and NaI yields the square planar complexes cis‐[PtX2{(PhSCH2)2SiPh2}] (2b, X = Br; 2c, X = I). The new compounds, which are fluxional in solution, have been studied by multinuclear NMR techniques; the crystal structures of 2a‐c have been determined by X ray diffraction. This series allows to evaluate the trans‐influence of the halide ligands on the lengths of the Pt‐S bonds, which increase from 227.26(12) (2a), 228.46(13) (2b) to 229.96(15) (2c) pm due to a more pronounced trans‐influence of I compared with Br and Cl. Complexation of (PhSCH2)2SiPh2 (1a) on HgBr2 gives the distorted tetrahedral compound [HgBr2{(PhSCH2)2SiPh2}] (3), having a quite loose coordination of the ligand both in solution and in the solid state [Hg‐S = 291.88(2) pm]. Alternatively, the coordination around Hg may be described as distorted square pyramidal in the solid state, since to due to a weak intermolecular Hg···Br interaction [346.72(13) pm], a dimeric motif is formed. Furthermore, the functionalised cyclic silane (PhSCH2)2SiC4H6 (1b) has been prepared and co‐ordinated as chelating dithioether ligands to [PtCl2(PhCN)2] affording the dithioether complex cis‐[PtCl2{(PhSCH2)2SiC4H6)}] (4). The crystal structure of 4 has also been determined by an X‐ray diffraction study.
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