U. Belluco

Far-infrared study of palladium(II)–halogen complexes with chelating ligands containing nitrogen and σ carbon as donor atoms

I.r. spectra of palladium(II) halogeno-bridged complexes of the type [Pd(N–C)X]2= azobenzene-2-C,N; NN-dimethylbenzylamine-2-C,N; and 2-methoxy-3-NN-dimethylaminopropyl; X = Cl or (Br) have been recorded in the range (600–120 cm.–1). The bridging-halogen stretching frequencies are discussed on the basis of a planar asymmetric Pd[graphic omitted]Pd unit.Bridge-splitting reactions with mono- and bi-dentate ligands bearing nitrogen or phosphorous as donor atoms are reported and the structures of the resulting products are interpretated on the basis of their far-i.r. spectra. We have also established that the v(Pd–Cl) frequency in the products in the range 300–280 cm.–1 with chloride in the trans-position to the phenyl or alkyl groups.

Novel cationic palladium(II) and platinum(II) diolefin derivatives

The complexes [M(C10H12·OMe)X]2 and [M(C10H12·OMe) py X](M = PdII, PtII; C10H12OMe = dicyclopentadienemethoxide; X = Cl or Br) react with bidentate ligands L–L(1,2′,-bipyridyl, ethylenediamine, 1,2-bisdiphenyl-phosphinoethane) in various solvents to give stable salts of the cations [M(C10H12·OMe)(L–L)]+. The conductometric course of these reactions is reported. I.r. spectra are discussed to support the formulation of these cations, which bear both an alkyl and an olefin group linked to the central metal. Stability of such unusual d8 metal ion co-ordination is discussed in terms of chelating effect.