Oxidatively Induced Reductive Elimination from (tBu2bpy)Pd(Me)2: Palladium(IV) Intermediates in a One-Electron Oxidation Reaction

This communication describes studies of oxidatively induced C-C bond-forming reductive elimination from ((t)Bu(2)bpy)Pd-II(Me)(2). With the outer-sphere oxidant ferrocenium, the data are consistent with a mechanism involving Pd-III and Pd-IV intermediates, with C-C bond formation occurring from the latter. The reaction with Ag+ appears to proceed via a Pd-Ag+ adduct, which then undergoes inner sphere electron transfer to generate Pd-III. In contrast, the slower benzoquinone reaction forms ethane by a different pathway that does not involve methyl group scrambling and generates Pd-0 products.