Organopalladium(IV) complexes containing phosphine ligands, and the structure of the platinum(IV) complex [PtMe 3(bpy)(PPh 3)][O 3SCF 3] (bpy=2,2′-bipyridine)

Abstract

Solutions containing unstable organopalladium(IV) complexes of phosphines, [PdMe 3(bpy)(L)] + (L=PMePh 2, PMe 2Ph, PPh 3), are generated on reaction of PdIMe 3(bpy) with the phosphines in dichloromethane- d 2. The complex [PdMe 3(bpy)(PPh 3)] + may also be formed quantitatively on the reaction of PdMe 2(bpy) with methyl triflate and triphenylphosphine in acetone- d 6. A solution of the platinum(IV) analogue [PtMe 3(bpy)(PPh 3)][O 3SCF 3] is formed following a similar procedure and isolated as crystals on reaction of PtIMe 3(bpy) with silver triflate followed by PPh 3. An X-ray structure determination of the platinum(IV) complex shows the fac-PtMe 3 configuration for octahedral [PtMe 3(bpy)(PPh 3)] +, 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.