Thermal analysis of coordination compounds. Part 3. Thermal decomposition of platinum complexes containing triphenylphosphine, triphenylarsine and triphenylstibine

Studies by thermogravimetric analysis (TG) and differential thermal analysis (DTA) of the complexes [PtCl2L2] (L is PPh3, AsPh3, SbPh3), [PtLn] (n = 3, L is SbPh3; n = 4, L is PPh3, AsPh3); [(PtL3)2N2]; [(PtL3)2C2] and [Pt(CO)2L2] (L is SbPh3) are described. Analysis of the TG and DTA curves showed that Pt(II) complexes of the type [PtCl2L2] have a higher thermal stability than the corresponding Pt(0) complexes of the type [PtLn], with the exception of [Pt(SbPh3)3], which is more stable than [PtCl2(SbPh3)2]. Thermal stabilities of each of the complexes are compared with those of the others in the series. Mechanisms of thermal decomposition of complexes of the types [PtCl2L2] and [PtLn] are proposed. Residues of the samples were characterized by chemical tests and IR spectroscopy. The residue from the thermal decomposition of [PtCl2L2] (L is PPh3, AsPh3) and [Pt(PPh3)4] is metallic platinum. For [Pt(AsPh3)4] the residue is a mixture of Pt and As, whereas for the complexes containing SbPh3 the residues are mixtures of Pt and Sb. In these cases, the proportional contents of Pt and As or Pt and Sb correspond to the stoichiometry of these elements in the respective complexes. The complexes {[Pt(SbPh3)3]2N2}, {[Pt(SbPh3)3]2C2} lose N2 or the ethynediyl group at 130-150°C and are transformed into [Pt(SbPh3)3]. © 1995.

Compostos de paládio(II) contendo ligantes sulfurados: síntese, caracterização e investigação da atividade biológica

This work deals with the synthesis, spectroscopic characterization of mono and polynuclear Pd(II) compounds obtained from the reaction between [PdCl2(MeCN)2] precursor and imidazolidine-2-thione (L1) and benzimidazoline-2-thione (L2). The interaction between [PdCl2(MeCN)2] and imidazolidine-2-thione, in the 1:2 molar ratio, using MeOH as solvent, yielded compound [Pd2Cl4(L1)4]Cl2 (1) whereas the complex [Pd2Br4(L1)4]Br2 (2) was obtained from the reaction between 1 and Br- ions. Binuclear compounds of general formulae [Pd2(L2)4]X23/2 MeOH {X= Cl-(3), Br-(4)} were synthesized using benzimidazoline-2-thione as ligand, employing the same procedure used in the synthesis of 1 and 2, respectively. The new complexes 1-4 are crystalline, air stable and soluble in methanol and dmso. The compounds were characterized by elemental analysis, IR spectroscopy, ESI/MS mass spectrometry and thermogravimetry. Coordination of the ligands L1 and L2 via sulphur atom was evidenced by the shift of the CS band (~499 cm-1, 1 and 2; ~620 cm-1, 3 and 4) to lower frequencies in comparison with those found in the free ligands (510 cm-1, L1; 660 cm-1, L2), indicating the weakening of the CS bom after coordination. ESI/EM mass spectra (positive mode) of the complexes 1-4 allowed atribute the molecular formulae [Pd2X4(L1)4]X2 {X= Cl-(1), Br-(2)} and [Pd2(L2)4]X2 {X= Cl-(3), Br-(4)} by the appearance of the peaks at m/z 794,61 [(1) + MeOH]+, m/z 836,77 [(2) - 2H - L1]+, m/z 810 [(3) - 2Cl]+, m/z 810 [(4) - 2Br]+. The TG-DTA curves showed that the complexes 1 and 2 are thermally stable up to 212 and 169º C, respectively, and further decompose to metallic palladium at 527º C (1, obt. 28,46 %; calcd. 27,88%) and 895º C (2, obt. 22,85 %; calcd. 22,62%). Compounds 3 and 4 exhibited an initial mass loss of ~5% between 25 -146º C related to the release of metanol molecules. The complexes 3...Fujimura Leite.

Modificação de eletrodos de carbono vítreo e nanotubos de Ti/TiO2 com aspirinato de cobre (II) para detecção eletroquímica e redução fotoeletrocatalítica de íons nitrito

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Compostos de Pd(II) contendo ligantes N,S-doadores: síntese, caracterização e estudo da atividade citotóxica

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)