The reactions of various α-tetraloneketimines(L) with palladium acetate in CHCl3 have been studied. In all cases acetato-bridged dimeric compound [Pd2L2(OAc)2] were obtained in which metallation had occurred at theperi position of the α-tetralone nucleus. The analogous chloro-bridged compounds [Pd2L2Cl2] were prepared from acetato-bridged dimer by metathesis reaction using LiCl. The bridge-splitting reaction of [Pd2L2Cl2] with triphenylphosphine, acetylacetone, methylacetoacetate, diethyldithiocarbamate, 2,2′-bipyridine, 1,10-phenanthroline, 4,4′-bipyridine and 2,2′-penta and hexamethylenebipyridine have been studied. The reactivity of 4,4′-bipyridine and 2,2′-penta and hexamethylenebipyridines have also been studied with di-μ-chlorobis[N,N-dimethylbenzylamine C2,N]dipalladium(II) and di-μ-chlorobis[N-benzylidenemethylamine C2,N] dipalladium(II). All the complexes obtained were characterised by elemental analysis, IR,1H NMR and13C NMR spectroscopy.