Organopalladium(IV) complexes containing phosphine ligands, and the structure of the platinum(IV) complex [PtMe3(bpy)(PPh3)][O3SCF3] (bpy=2,2′-bipyridine)

Solutions containing unstable organopalladium(IV) complexes of phosphines, [PdMe3(bpy)(L)]+ (L=PMePh2, PMe2Ph, PPh3), are generated on reaction of PdIMe3(bpy) with the phosphines in dichloromethane-d2. The complex [PdMe3(bpy)(PPh3)]+ may also be formed quantitatively on the reaction of PdMe2(bpy) with methyl triflate and triphenylphosphine in acetone-d6. A solution of the platinum(IV) analogue [PtMe3(bpy)(PPh3)][O3SCF3] is formed following a similar procedure and isolated as crystals on reaction of PtIMe3(bpy) with silver triflate followed by PPh3. An X-ray structure determination of the platinum(IV) complex shows the fac-PtMe3 configuration for octahedral [PtMe3(bpy)(PPh3)]+, and supports the assignment of identical structures for the unstable palladium(IV) complexes from comparison of 1H- and 13P-NMR spectra of palladium(IV) and platinum(IV) complexes.