Some new coordination polymers of Mn(II),
Co(II), Ni(II), Cu(II), Zn(II) and Cd(II), obtained from the interaction of
metal acetate with dipotassium salt of N,N’-di(carboxyethylidene)terephthalaldehydediimine
(K2SB) are described. The products, which have been
characterized by elemental analyses, magnetic measurements, thermogravimetric
analyses, electronic and infrared spectral studies, have composition, [M(SB)(H2O)2]n. These colored coordination polymers are non-hygroscopic and quite stable
at room temperature. On the basis of analytical data and IR studies, a 1:1
metal to ligand stoichiometry has been suggested to these coordination polymers.
The IR studies have also revealed that ligands are coordinated to metal ion
through carboxy oxygen and azomethine nitrogen. All the studies suggested
tetradentate nature of the ligand with octahedral symmetry of the coordination
polymers. All the coordination polymers are insoluble in acetone, ethanol,
chloroform, methanol, benzene, DMF and DMSO. The thermal decomposition of
the coordination polymers is studied and indicates that not only the coordinated
water is lost but also that the decomposition of the ligand from the coordination
polymers is necessary to interpret the successive mass loss.
Authors:Gurdip Singh, A. K. Shrimal, Inder Pal Singh Kapoor, Chandra Prakash Singh, Dinesh Kumar, and Manan S. Mudi
propellants compositions. Nickel hydrazine nitrate has been prepared and found insensitive to impact, friction, or electrostatic charge, but more sensitive to flame [ 5 ]. Transitionmetal complexes are also used to obtain nano size metal oxides, which can
Transition metal dithiocarbamate complexes, [M(S2CN(C2H5)(CH2CH2OH)] (M=Co, Ni, Cu, Zn and Cd) have been prepared and characterized by elemental analysis and infrared spectra. Thermal decomposition
of all the complexes occurs in two or three stages. The first stage in all the complexes is always fast with 65-70% mass loss.
In all cases the end product is metal oxide except in the case of cobalt complex which gives Co metal as an end product. During
decomposition of copper complex, first CuS is formed at ~300C which is converted into CuSO4 and finally CuO is formed. However, decomposition in helium atmosphere yields CuS. SEM studies of transition metal dithiocarbamates
reveal needle shape crystalline phase at room temperature and formation of metal sulphide/oxide at higher temperatures. The
activation energy varies in a large range of 33.8-188.3 kJ mol-1, being minimum for the Cu complex and maximum for the Zn complex possibly due to d10 configuration. In the case of Ni, Zn and Cd complexes the order of reaction is two suggesting bimolecular process involving
intermolecular rearrangement. However, in other cases it is a unimolecular process. Large negative values of ΔS# for all the complexes suggest that the decomposition process involves rearrangement.
Authors:F. J. Caires, L. S. Lima, C. T. Carvalho, A. B. Siqueira, Oswaldo Treu-Filho, and M. Ionashiro
have been used to characterize complexes of bivalent transitionmetal ions [ 9 , 10 ]. However, they are not found in the literature thermal studies involving all metal-ions with oxamates, as well as the characterization of the gaseous products
Authors:S. Shakshooki, L. Szirtes, and Yu. Yakovlev
Mixed zirconium-titanium phosphates were synthesized by various methods and under various conditions. The effect of these conditions on the selectivity of synthetized samples toward the transition metal ions was investigated. It was found that the kd values are independent of the metal concentration and they give the selectivity order Zn2+>Cu2+
Authors:V. Logvinenko, L. Yudanova, N. Yudanov, and G. Chekhova
The thermal decomposition of salts (both normal and acid) of transition metals with carboxylic acids (maleic, ortho-phthalic
and terephthalic) was studied in inert atmosphere. The residues after pyrolysis (up to 450C) are composites including two
structural components: an organic polymer matrix and spherical conglomerates from metal grains coated with polymer. Thermal
decomposition of solid solutions of metal bimaleates (Co-Ni, Fe-Ni, Zn-Ni) was investigated. Thermogravimetric data (obtained
at different rates of linear heating) were processed with 'Netzsch Thermokinetics' computer program. Kinetic parameters were
calculated only for the first decomposition step, and the process is described by Prout-Tompkins equation of nth order with autocatalysis. Some properties of the resulting composites have been studied qualitatively.
Authors:S. Vairam, T. Premkumar, and S. Govindarajan
New dihydrazinium divalent transition metal trimellitate hydrates of empirical formula (N2H5)2M(Html)2·nH2O, where n = 1 for M = Co or Ni, and n = 2 for M = Mn, Zn, or Cd (H3tml = trimellitic acid), and monohydrazinium cadmium trimellitate, [(N2H5)Cd(Html)1.5·2H2O] have been prepared and characterized by physico-chemical methods. Electronic spectroscopic, and magnetic moment data suggest
that Co and Ni complexes adopt an octahedral geometry. The IR spectra confirm the presence of monodentate carboxylate anion
(Δν = νasy(COO−) − νsym(COO−) > 190 cm−1) and coordinated N2H5+ ion (νN–N 1015 − 990 cm−1) in all the complexes. All the complexes undergo endothermic decomposition eliminating CO2 in the temperature region 200–250 °C, followed by exothermic decomposition (in the range of 500–570 °C) of organic moiety
to give the respective metal carbonate as the end products except nickel and cobalt complexes, which leave respective metal
oxides. X-ray powder diffraction patterns reveal that Ni and Co complexes are isomorphous as are those of, Zn(II) and Cd(II)
of the type, (N2H5)2M(Html)2·2H2O.
New divalent transition metal 3,5-pyrazoledicarboxylate
hydrates of empirical formula Mpz(COO)2(H2O)2,
where M=Mn, Co, Ni, Cu, Zn and Cd (pz(COO)2=3,5-pyrazoledicarboxylate),
metal hydrazine complexes of the type Mpz(COO)2N2H4
where M=Co, Zn or Cd and Mpz(COO)2nN2H4H2O,
where n=1 for M=Ni
and n=0.5 for M=Cu
have been prepared and characterized by physico-chemical methods. Electronic
spectroscopic data suggest that Co and Ni complexes adopt an octahedral geometry.
The IR spectra confirm the presence of unidentate carboxylate anion (Δν=νasy(COO–)–νsym(COO–)>215
cm–1) in all the complexes and bidentate
bridging hydrazine (νN–N=985–950 cm–1)
in the metal hydrazine complexes. Both metal carboxylate and metal hydrazine
carboxylate complexes undergo endothermic dehydration and/or dehydrazination
followed by exothermic decomposition of organic moiety to give the respective
metal oxides as the end products except manganese pyrazoledicarboxylate hydrate,
which leaves manganese carbonate. X-ray powder diffraction patterns reveal
that the metal carboxylate hydrates are isomorphous as are those of metal
hydrazine complexes of cobalt, zinc and cadmium.
decomposition of transition metal malonates, MCH2C2O4⋅xH2O and transition metal
succinates, M(CH2)2C2O4⋅xH2O (M=Mn,
Fe, Co, Ni, Cu, Zn) has been studied employing TG, DTG, DTA, XRD, SEM, IR
and Mssbauer spectroscopic techniques. After dehydration, the anhydrous
metal malonates and succinates decompose directly to their respective metal
oxides in the temperature ranges 310–400 and 400–525C, respectively.
The oxides obtained have been found to be nanosized. The thermal stability
of succinates have been found to be higher than that of the respective malonates.