• S Govindarajan

      Articles written in Journal of Chemical Sciences

    • Dipicolinate complexes of main group metals with hydrazinium cation

      K Saravanan S Govindarajan

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      Some new coordination complexes of hydrazinium main group metal dipicolinate hydrates of formulae (N2H5)2M(dip)2.nH2O (where, M = Ca,Sr,BaorPb andn = 0, 2, 4 and 3 respectively and dip = dipicolinate), N2H5Bi(dip)2.3H2O and (N2H5)3Bi(dip)3.4H2O have been prepared and characterized by physico-chemical techniques. The infrared spectra of the complexes reveal the presence of tridentate dipicolinate dianions and non-coordinating hydrazinium cations. Conductance measurements show that the mono, di and trihydrazinium complexes behave as 1:1, 2:1 and 3 :1 electrolytes respectively, in aqueous solution. Thermal decomposition studies show that these compounds lose water followed by endothermic decomposition of hydrazine to give respective metal hydrogendipicolinate intermediates, which further decompose exothermically to the final product of either metal carbonates (Ca, Sr, Ba and Pb) or metal oxycarbonates (Bi). The coordination numbers around the metal ions differ from compound to compound. The various coordination numbers exhibited by these metals are six (Ca), seven (Ba), eight (Sr) and nine (Pb and Bi). In all the complexes the above coordination number is attained by tridentate dipicolinate dianions and water molecules. The X-ray diffraction patterns of these compounds differ from one another suggesting that they are not isomorphous.

    • Preparation, spectral and thermal studies of pyrazinecarboxylic acids and their hydrazinium salts

      T Premkumar S Govindarajan Wei-Ping Pan

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      Some new hydrazinium 2-pyrazinecarboxylate and 2,3-pyrazinedi-carboxylate salts of the formulae N2H5pc, N2H5pc.H2O (Hpc = 2-pyrazinecarboxylic acid), N2H5Hpdc, (N2H5)2pdc.H2O and N2H5(Hpdc).H2pdc (H2pdc = 2,3-pyrazinedi-carboxylic acid) have been prepared by neutralization of aqueous hydrazine hydrate with the respective acids in appropriate molar ratios. The free acids and their hydrazinium salts have been characterized by analytical, IR spectroscopic and thermal studies. IR spectra of all the salts show N-N stretching frequencies of the N2H5+ ion in the region 975–960 cm-1. The thermoanalytical behaviour of the free acids and their salts has been investigated by simultaneous TG and DTA. While pyrazinecarboxylic acid shows single-step endothermic (229°C) complete decomposition, pyrazindi-carboxylic acid shows exothermic decarboxylation followed by identical endothermic decomposition as that of the former. Similarly, salts of the monocarboxylic acid show endothermic effects during pyrolysis, whereas salts of the dicarboxylic acid show endothermic followed by exothermic decomposition. The acids and their salts both undergo complete decomposition to gaseous products.

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