The action of Pd(AcO)2 on the imines C6RmH5-mCH=N(CH2)nC6H5 have been studied. Five-membered endo metallacyles were obtained from the imines 1a (R = 3,5-F2, n = 0), 1b (R = 3,5-F2, n = 1), 1c (R = 3,5-(MeO)2, n = 0) and 1d (R = 3,5-(MeO)2, n = 1), by activation of a C(aromatic)-H bond, in spite of the presence of MeO or F substituents on the carbon atom adjacent to the metallation position. 1H NMR spectra of the acetate bridged compounds [Pd(C-N)(μ-AcO)2] (2a-d) obtained show the existence of different isomers in solution. Complexes [PdBr(C-N)(PPh3)] (4) and [PdBr(C-N)(PPh3)2] (5) can be obtained by the action of PPh3 on the new cyclometallated compounds. [Pd(3,5-F2C6H2CH=NC6H5)Br(PPh3)2] crystallizes in the space group P21a with a = 20.224(4), b = 17.447(3), c = 12.290(2) Å, β = 110.12(3)° and Z = 4. The dihedral angle between the metallated phenyl ring and the coordination plane is 86.6°. An N=CH proton and a fluorine atom ortho to the Pd-C bond occupy the apical positions in the coordination sphere of the palladium atom.