Heating a suspension of the monomeric hydroxo palladium complex of the type [Pd(N-N)(C(6)F(5))(OH)](N-N = bipy, Me(2)bipy, phen or tmeda) in methylketone (acetone or methylisobutylketone) under reflux affords the corresponding ketonyl palladium complex [Pd(N-N)(C(6)F(5))(CH(2)COR)]. On the other hand, the reaction of the hydroxo palladium complexes [Pd(N-N)(C(6)F(5))(OH)](N-N = bipy, phen or tmeda) with diethylmalonate or malononitrile yields the C-bound enolate palladium complexes [Pd(N-N)(CHX(2))(C(6)F(5))](X = CO(2)Et or CN), and the reaction of [Pd(N-N)(C(6)F(5))(OH)](N-N = bipy or phen) with nitromethane gives the nitromethyl palladium complexes [Pd(N-N)(CH(2)NO(2))(C(6)F(5))]. [Pd(tmeda)(C(6)F(5))(OH)] catalyses the cyclotrimerization of malononitrile. The crystal structures of [Pd(bipy)(C(6)F(5))(CH(2)COMe)].1/2Me(2)CO, [Pd(tmeda)(C(6)F(5))[CH(CO(2)Et)(2)]], [Pd(tmeda)(C(6)F(5))[CH(CN)(2)]] and [Pd(tmeda)(C(6)F(5))(CH(2)NO(2))].1/2CH(2)Cl(2) have been established by X-ray diffraction.