One-dimensional heteropolynuclear tetracyanopalladate(II) complexes: Syntheses, crystal structures, thermal analyses and spectroscopic investigations (original) (raw)
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Anodic oxidation of Co, Cu, Zn, and Sn metals in an acetone solution of 1,1-malonayl-bis(4-p-Chloro-phenylthiosemicarbazide) yields complexes of composition with general formula [Co 2 (pClMaTS)(H 2 O) 6 ]•2H 2 O, [Cu 2 (pClMaTS)(H 2 O) 6 ], [Zn 2 (pClMaTS)(H 2 O) 6 ] and [Sn 2 (pClMaTS)(H 2 O) 6 ]•2H 2 O. Chelation was investigated based on elemental analysis, conductivity, magnetic moment, spectral (UV-Vis, IR, Raman, 1 HNMR, mass), thermal, and ESR studies. The Raman and infrared spectral studies suggests the tridentate behavior of the ligand from each tail. Since the ligand has two thiosemicarbazide groups, it may acts in an SNO tridentate fashion from each side with one of the two metal ions forming a polynuclear complex coordinating through both of the lone pair of electrons the enolic oxygen of the carbonyl group (C=O), the azomethine nitrogen (C=N) and the thioenol form of the thiocarbonyl group (C=S). The differential thermogravimetric analysis (DTG) curves were used to study the decomposition steps of the isolated complexes using Horowitz-Metzger (HM) and Coats-Redfern (CR) methods. The kinetic thermodynamic parameters such as: E*, ∆H*, ∆S*and ∆G* are calculated from the DTG curves.
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The iron(II) complex of the Schiff bases trans-N,N'-bis(salicylidene)-1,2-cyclohexanediamine (Salcn), manganese(II) and vanadyl complexes of the Schiff bases cis-and trans-N,N'-bis(salicylidene)-1,2-cyclohexanediamine (Salcn) were prepared and characterized by IR spectroscopy, and elemental analysis. These new complexes were submitted to thermal analysis (TG and DSC) under dynamic air atmosphere. The differences in the decomposition profiles were related to the structure of isomers and decomposition intermediates were characterized according to their X-ray diffraction pattern and by their infrared spectrum.
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Three new heterometallic complexes, [Cu(N-Meim)4Pd(μ-CN)2(CN)2]n (1), [Zn(N-Meim)3Pd(μ-CN)2(CN)2]n (2) and [Cd(N-Meim)2Pd(μ-CN)4]n (3), have been isolated from the reactions of M[Pd(CN)4] (M = Cu(II), Zn(II) or Cd(II)) and N-Meim (N-methylimidazole) with in different molar ratios. All complexes have been characterized by X-ray analyses, vibrational (FT-IR and Raman) spectra, thermal and elemental analyses. The crystallographic analysis reveals that the crystal structures of 1 and 2 are 1D coordination polymer, while 3 presents a 2D network. In the Cu(II) and Zn(II) complexes, two cyanide groups of [Pd(CN)4]2− coordinated to the adjacent M(II) ions and distorted octahedral and square pyramidal geometries of complexes are completed by four and three nitrogen atoms of N-Meim ligands, respectively. The Cd(II) ion is six-coordinate, completed with the two nitrogen atoms of N-Meim ligands in the axial positions and the four nitrogen atoms from bridging cyano groups in the equatorial plane. The most striking features of complexes 1–3 are the presence of obvious C–H⋯Pd hydrogen-bonding interactions between the Pd(II) and hydrogen atoms of N-Meim ligand. This weak hydrogen bonding plays a crucial role in the architecture of the network polymers. The adjacent chains are held together by C–H⋯Pd, C–H⋯π or π⋯π interactions, forming three-dimensional network.Three new heterometallic complexes, [Cu(N-Meim)4Pd(μ-CN)2(CN)2]n (1), [Zn(N-Meim)3Pd(μ-CN)2(CN)2]n (2) and [Cd(N-Meim)2Pd(μ-CN)4]n (3), have been isolated from the reactions of M[Pd(CN)4] (M = Cu(II), Zn(II) or Cd(II)) and N-Meim (N-methylimidazole) with in different molar ratios. The most striking features of complexes are the presence of obvious C−H···Pd hydrogen-bonding interactions between the Pd(II) and hydrogen atoms of N-Meim ligand. This weak hydrogen bonding plays a crucial role in the architecture of the network polymers. The adjacent chains are held together by C–H⋯Pd, C–H⋯π or π⋯π interactions, forming three-dimensional network.
Natural Science, 2011
Anodic oxidation of Co, Cu, Zn, and Sn metals in an acetone solution of 1,1-malonayl-bis(4-p-Chloro-phenylthiosemicarbazide) yields complexes of composition with general formula [Co 2 (pClMaTS)(H 2 O) 6 ]•2H 2 O, [Cu 2 (pClMaTS)(H 2 O) 6 ], [Zn 2 (pClMaTS)(H 2 O) 6 ] and [Sn 2 (pClMaTS)(H 2 O) 6 ]•2H 2 O. Chelation was investigated based on elemental analysis, conductivity, magnetic moment, spectral (UV-Vis, IR, Raman, 1 HNMR, mass), thermal, and ESR studies. The Raman and infrared spectral studies suggests the tridentate behavior of the ligand from each tail. Since the ligand has two thiosemicarbazide groups, it may acts in an SNO tridentate fashion from each side with one of the two metal ions forming a polynuclear complex coordinating through both of the lone pair of electrons the enolic oxygen of the carbonyl group (C=O), the azomethine nitrogen (C=N) and the thioenol form of the thiocarbonyl group (C=S). The differential thermogravimetric analysis (DTG) curves were used to study the decomposition steps of the isolated complexes using Horowitz-Metzger (HM) and Coats-Redfern (CR) methods. The kinetic thermodynamic parameters such as: E*, ∆H*, ∆S*and ∆G* are calculated from the DTG curves.
Journal of Thermal Analysis and Calorimetry
Four new mononuclear Pd(II) complexes of the type [PdX2(tdmPz)] {X = Cl− (1); Br− (2); I− (3); SCN− (4); tdmPz = 1-thiocarbamoyl-3,5-dimethylpyrazole} have been synthesized and characterized by elemental analysis, IR spectroscopy, 1H and 13C{1H}-NMR experiments. The thermal behavior of the complexes 1–4 has been investigated by means of thermogravimetry (TG) and differential thermal analysis (DTA). From the initial decomposition temperatures, the thermal stability of the complexes can be ordered in the sequence: 3 < 4 ≡ 2 < 1. The final products of the thermal decompositions were characterized as metallic palladium by X-ray powder diffraction.