Syntheses and Crystal Structures of New Palladium(II) and Platinum(IV) Trialkylsulfonium Compounds

The reactions of platinum(II) iodide with triethyl‐ or trimethylsulfonium iodide in acetonitrile solution lead to the formation of crystalline products (Et 3 S) 2 [PtI 6 ] ( 1 ) and [Me 3 S] 2 [PtI 6 ]·CH 3 CN ( 2 ), respectively. The formation of Pt(IV) complexes may be explained either by disproportionation of PtI 2 or oxidation by oxygen. Palladium(II) iodide reacts with triethylsulfonium iodide to give the palladium(II) complex (Et 3 S) 2 [PdI 4 ] ( 3 ). The crystal structures of 1 – 3 were determined by single‐crystal X‐ray diffraction. In the crystal structures, the compounds 2 and 3 exhibit an extensive hydrogen‐bonding network.