• S Vancheesan

      Articles written in Journal of Chemical Sciences

    • Hydrogenation of olefinic substrates in aqueous and aqueous-organic biphase systems using rhodium complex of sulphonated triphenyl phosphine

      V R Parameswaran S Vancheesan

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      Water-soluble meta sulphophenyldiphenylphosphine complex of rhodium preparedin situ catalyses the homogeneous hydrogenation of fumaric, maleic and crotonic acids in water and 1:1 water-methanol mixture as solvents. Fumaric acid gives a higher rate of hydrogenation than maleic acid. Rate of hydrogenation also increases on changing the solvent from pure water to 1:1 mixture of methanol and water. Rate law for the reaction has been proposed.

    • Reactions of Mo(CO)6 under biphase conditions

      T Chandiran S Vancheesan

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      The reaction between molybdenum hexacarbonyl and hydroxide ion under solid-liquid biphase conditions at room temperature gave [(CO)3Mo(-OH)3Mo(CO)3]3−. Tetrabutylammonium bromide was used as the phase transfer agent. The reaction between hydroxide ion and molybdenum hexacarbonyl under liquid-liquid or solid-liquid biphase conditions did not give any hydrido complex. Hydroxide ion catalysed substitution reactions of molybdenum hexacarbonyl were studied under solid-liquid and liquid-liquid biphase conditions. The reaction between molybdenum hexacarbonyl and tetrabutylammonium hydroxide in dichloromethane at room temperature was studied by infrared spectroscopy. Based on the experimental evidence, a mechanism is suggested for the substitution reactions catalysed by the hydroxide ion under biphase conditions.

    • Synthesis and characterisation of cyclopalladated complexes of α-tetraloneketimine

      K Selvakumar S Vancheesan

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      The reactions of various α-tetraloneketimines(L) with palladium acetate in CHCl3 have been studied. In all cases acetato-bridged dimeric compound [Pd2L2(OAc)2] were obtained in which metallation had occurred at theperi position of the α-tetralone nucleus. The analogous chloro-bridged compounds [Pd2L2Cl2] were prepared from acetato-bridged dimer by metathesis reaction using LiCl. The bridge-splitting reaction of [Pd2L2Cl2] with triphenylphosphine, acetylacetone, methylacetoacetate, diethyldithiocarbamate, 2,2′-bipyridine, 1,10-phenanthroline, 4,4′-bipyridine and 2,2′-penta and hexamethylenebipyridine have been studied. The reactivity of 4,4′-bipyridine and 2,2′-penta and hexamethylenebipyridines have also been studied with di-μ-chlorobis[N,N-dimethylbenzylamine C2,N]dipalladium(II) and di-μ-chlorobis[N-benzylidenemethylamine C2,N] dipalladium(II). All the complexes obtained were characterised by elemental analysis, IR,1H NMR and13C NMR spectroscopy.

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