Thesis (Ph.D.) - Cairo University - Faculty of Science - Department of Inorganic chemistry

A series of new binary platinum(II), ternary platinum(II), palladium(II), and ruthenium(II) complexes have been synthesized and characterized. The ternary complexes separated were of the type [M₁(L₁-₄)Cl₂].xH₂O, [M₂(L₁-₄)ox].xH₂O, and [(M₃L₁-₄)₂æPPi].xH₂O where M₁=Pt(II), M₂=Pt(II), Pd(II), and Ru(II), M₃=Pd(II), Ru(II), L=formamidine ligands, ox=oxalate and PPi= inorganic pyrophosphate were synthesized and characterized by elemental analyses, magnetic susceptibility, UV-Vis, infrared (IR), mass spectroscopy, thermal analysis and theoretical calculations. Comparison of the IR spectra of the free ligands and their metal complexes confirmed that the formamidines act as bidentate N2 ligands and the (ox, PPi) as bidentate O2 ligands. Ru(III) has been reduced to Ru(II) in the reaction with the formamidine ligands. The complexes are diamagnetic and the electronic spectral data showed the peaks due to square planar Pt(II) and Pd(II) complexes, whereas Ru(II) were octahedral complexes. Mass spectroscopy and thermal analysis indicate monomer complexes for all binary and ternary Pt(II) complexes. Pd(II) and Ru(II) ternary complexes with oxalate are also monomers. The ternary complexes of pyrophosphate with Pd(II) and Ru(II) were found to be dimmers. Thermal studies reveal a general decomposition pattern, whereby the complexes decomposed partially in many steps due to loss of the water, chlorine atoms, carbon oxides, P₂O₇, organic moiety, the oxygen atom and leave metals as residue. The activation energies, E*, entropies, xS*, enthalpies, xH* and Gibbs free energies, xG*, of the thermal decomposition stages have been calculated from thermogravimetric (TGA) and derivative thermogravimetric (DrTGA) curves, using Coats-Redfern and Horowitz- Metzger methods. The metal complexes are neutral, stable, non-hygroscopic

Issued also as CD