The N-perfluoro-phenylated pyridyldiamine (H2N2Npy)-N-PFP (1) has been prepared by a palladium-catalyzed coupling of hexafluorobenzene and the diamine (H2NCH2)(2)C(CH3)(2- C5H4N) using the palladacycle trans-di(p-acetato)bis[o-(di-o-tolylphosphino)benzyl]palladium(II) as catalyst. Reactions of (H2N2Npy)-N-PFP and Zr(NMe2)(4) at room temperature or 90 degrees C led to the complexes [((NN2Npy)-N-PFP-N-TFAP)ZrF(NMe2)] (2) and [((N2Npy)-N-TFAP)ZrF2] (3) in which one or two dimethylamido groups replaced one or two ortho fluorine atoms of the pentafluorophenyl groups in the ligand. Reaction of Me3SiX (X = Cl, I) with [((N2Npy)-N-TFAP)ZrF2] (3) resulted in the formation of mixed halogenated complexes [((N2Npy)-N-TFAP)ZrFI] (4) and [((N2Npy)-N-TFAP)ZrFCl] (5) in which the axially bound fluorido 4and is substituted. Reaction of [(N2TFAPNpy)ZrF2] (3) with LiNHNPI-12 afforded the monohydrazido(1) complex [(1-)2(TFAP)N(py))ZrF(NHNPh2)] (6) Which was converted to the dimeric fluoro-potassium bridged.hydrazinedado complex [Zr((N2Npy)-N-TFAP)FNNPh2K](2) (7) using KHMDS. The corresponding reaction with LiHMDS yielded the monomeric, donor free complex [Zr((N2Npy)-N-TFAP)NNPh2] (8).