Cationic thiolate and selenolate complexes of platinum(IV)

Article abstract of DOI:10.1139/v01-187

The reaction of the adamantanoid compounds [Hg₄(EPh)₆(L)₄][ClO₄]₂ (E = S or Se, L = PEt₃ or PPh₃) with [PtMe₂(bu₂bpy)] (bu₂bpy = 4,4′-di-tert-butyl-2,2′-bipyridine) occurs easily to give the first examples of cationic thiolate or selenolate derivatives of platinum(IV), [PtMe₂(EPh)L(bu₂bpy)][ClO₄], and the addition is shown to occur with trans stereochemistry. The new complexes are characterized by NMR spectroscopy and when L = PEt₃ by X-ray structure determinations. When L = PPh₃, a competitive reaction leads to methyl group transfer from platinum to mercury to give MeHgEPh (E = S or Se).