Co-ordination chemistry of higher oxidation states. Part 3. Palladium(IV) complexes with neutral unidentate ligands

Abstract

Oxidation of [NR₄][PdLX₃] with the corresponding halogen (X₂) in carbon tetrachloride gave octahedral palladium(IV) anions [NR₄][PdLX₅][L = py (pyridine), AsEt₃, SMe₂, or SeMe₂, X = Cl or Br; L = NMe₃, PPh₃S, or PPrⁿ₃, X = Cl; L = PEt₂Ph, X = Br]. Attempts to prepare analogues with L = SbMe₃, TeMe₂, or dmso (dimethyl sulphoxide) failed. Neutral palladium(IV) complexes trans-[PdL₂X₄](L = NMe₃, py, PPrⁿ₃, or AsMe₂Ph, X = Cl; L = NMe₃, X = Br) have been obtained from trans-[PdL₂X₂] and X₂. The complexes were characterised by i.r. and electronic spectroscopy, and conductivity measurements, and their thermal decomposition examined by t.g.a.