The reactions of the cationic complexes [Pd(η³-allyl)(N–N′)]ClO₄(allyl = 4-methoxycyclohexenyl, allyl or 2-methylallyl; N–N′= 1, 2-bis(imino)ethanes or pyridine-2-carbaldimines) with diethylamine, in the presence of an activated olefin, in chloroform at 25 °C have been studied. They involve a fast equilibrium displacement of the co-ordinated α-diimine to yield [Pd(η³-allyl)(NHEt₂)₂]⁺, accompanied by slow nucleophilic attack at the allyl ligand of the [Pd(η³-allyl)(N–N′)]⁺ substrate producing [Pd(η²-olefin)(N–N′)](olefin = dimethyl fumarate or fumaronitrile) and allyldiethylamine. As shown by the stereochemical course of the reaction with [Pd(1–3-η³-C₆H₈OMe)(C₅H₄N-2-CHNC₆H₄OMe4)]ClO₄, the nucleophilic attack takes place on the allyl face opposite the metal. The equilibrium constants for α-diimine displacement have been determined. They are strongly affected by the structure of the N–N′ ligand and decrease in the order RNCH–CHNR RNC(Me)–C(Me)NR ≈ C₅H₄N-2-CHNR > C₅H₄N-2-CHNCMe₃(R = C₆H₄OMe-4). Kinetic studies showed that the pseudo-first-order rate constants (k_obs) for the slow amination path display both a first- and second-order dependence on the NHEt₂ concentration of type k_obs=k₂[NHEt₂]+k₂′[NHEt₂]². The k₂ term is related to direct bimolecular attack of NHEt₂ on the terminal allyl carbon, whereas the k₂′ term is ascribed to a parallel nucleophilic attack by a hydrogen-bonded diethylamine dimer arising from amine self-association.