The Trimethylsulfonium Ion, [(CH₃)₃S]⊕, in Hexachlorometallate(IV) Complexes, [(CH₃)₃S]₂MCl₆ (M = Pt, Se, Te, Sn). ¹H NMR, ³⁵Cl NQR, and X‐Ray Diffraction Studies

The measurements of 35 Cl NQR spectra and X‐ray powder diffraction patterns were carried out in a series of the complexes of trimethylsulfonium hexachlorometallates(IV), (triMS) 2 MCl 6 (M = Pt, Se, Te, Sn). For (triMS) 2 TeCl 6 and (triMS) 2 SnCl 6 , 1 H NMR second moments were determined at various temperatures between 77 K and 370 K. The temperature dependence of 1 H NMR spin‐lattice relaxation times was observed for (triMS) 2 PtCl 6 , (triMS) 2 TeCl 6 , and (triMS) 3 SnCl 6 . From X‐ray powder patterns, it was found that the complexes studied are isomorphous with each other and form cubic crystals belonging to the space group T ‐Pa3. The unit cell dimensions were determined. A single 35 Cl NQR line was observed for all of the complexes in agreement with the crystal symmetry. From 1 H NMR studies, two kinds of motions of (triMS)⊕, namely, the intracationic CH 3 group reorientation and the reorientation of the whole cation about its C 3 axis, were observed separately in the above three complexes. The activation energies of these motions were evaluated and compared with those of trimethylammonium ions in hexahalometallate(IV) complexes previously reported.