Carbon–oxygen bond formation at organopalladium centres

The reaction of PdMe2(bpy) (bpy = 2,2′-bipyridine) with diaroyl peroxides is a complex process in which initial oxidation of Pd(II) is followed by methyl group exchange between an undetected Pd(IV) intermediate and PdMe2(bpy) to give PdMe(O2CAr)(bpy) and PdMe3(O2CAr)(bpy); the latter Pd(IV) complex decomposes by elimination of Me–Me to give additional PdMe(O2CAr)(bpy) which reacts with (ArCO2)2 to give Me–O2CAr and Pd(O2CAr)2(bpy). The complexes Pd(O2CPh)2(L2) (L2=bpy, N,N,N′,N′-tetramethylethylyenediamine) have been characterised by X-ray diffraction.