A new route to organopalladium(IV) complexes is described, involving replacement of bromine in the 2,2'-bipyridyl complex PdBrMe2(CH2Ph)(bpy), by other halogen or pseudohalogen groups. H-1 NMR studies of the decomposition of PdXMe2(CH2Ph)(bpy) in warm (CD3)2CO indicate that a selectivity in reductive elimination of alkanes occurs, to give ethane (X = Br, N3, NCS), or a mixture of ethane and ethylbenzene in ca. 9/1 ratio (X = F, Cl, I). The reductive elimination product azido(2,2'-bipyridyl)benzylpalladium(II) has been characterized by X-ray crystallography.