The compounds (L)PtMen where n-2 or 4 and L-mmb (1-methyl-(2-ethylthiomethyl)-1H-benzimidazole) or L-mtb (1-methyl-(2-tert-butylthiomethyl)-¹H-benzimidazole) were characterized by X-ray crystallography (except for (mtb)PtMe₂₎ and by¹H- and ¹⁹⁵ Pt-NMR spectroscopy. The etramethylplatinum(IV) complexes exhibit av ariable degree of dynamic ¹H-NMR beha vior due to the mobility at the thioether sulfur atom in the non-planar five-membered chelate ring, as supported by structural analysis.Density-functional theory (DFT) calculations were used to reproduce the structural features and the ¹H-NMR chemical shifts. In comparison with other late transition metal complexes of these N-S chelate ligands the Me₄Pt and especially the Me₂  Pt compounds exhibit a relatively stronger preference of the metal for the sulfur donor.