The action of palladium(II) acetate on the primary amines 2-phenylaniline and (R)-α-methylbenzylamine and subsequent treatment with LiBr allows the preparation of the corresponding cyclopalladated dimers [P)Br]2 (1a and 1b respectively). Mononuclear compounds [P)Br(L)], , have ben obtained by reaction of 1 with py-d5 and PPh3. Addition of PPh3 to chloroform solutions of 2 produces a rapid exchange between coordinated and free PPh3. 31P{1H} NMR at variable temperature suggests that this exchange proceeds for 2a through the fast equilibrium [Pd(CN)Br(PPh3)2]⇔[P)Br(PPh3)], while the usual mechanism in substitution reactions in d8 planar square complexes is involved in the case of 2b. The X-ray crystal structure of 2a has been determined. 2a crystallizes in the triclinic space group with .