Carbon-oxygen bond formation at organopalladium centres

The reaction of PdMe2(bpy) (bpy = 2,2'-bipyridine) with diaroyl peroxides i s a complex process in which initial oxidation of Pd(II) is followed by met hyl 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) whic h reacts with (ArCO2)(2) to give Me-O2CAr and Pd(O2CAr)(2)(bpy). The comple xes Pd(O2CPh)(2)(L-2) (L-2 = bpy, N. N, N', N'-tetramethylethylyenediamine) have been characterised by X-ray diffraction. (C) 2001 Elsevier Science B. V. All rights reserved.