• K Mohan

      Articles written in Journal of Chemical Sciences

    • Kinetics of oxidation of ethylenediamine tetraacetic acid by aromatic N-bromamines in buffer medium

      K Mohan S Ananda D S Mahadevappa

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      Kinetics of oxidation of disodium ethylene-diamine-tetraacetic, acid (EDTA) by bromamine-B (BAB) and bromamine-T (BAT) was investigated at 30°C in acetate buffer of pH 5. The oxidation behaviour is similar, with a first-order dependence of rate on [oxidant] and fractional orders in [EDTA] and [H+]. The influence of the reaction products, halide ions, ionic strength and dielectric constant of medium on the rate has been studied. A possible mechanism is suggested.

    • Oxidation of secondary alcohols by sodium N-bromobenzene-sulphonamide: A kinetic study

      K Mohan D S Mahadevappa Puttaswamy

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      The kinetics of oxidation of 2-propanol, 2-butanol, 2-pentanol, 2-hexanol and 2-heptanol to the respective ketones by sodium N-bromobenzenesulphonamide (bromamine-B) in presence of HCl was studied at 40°C. The rate shows a first-order dependence on both [oxidant]0 and [alcohol]0 and is fractional in [H+] and [Cl]. The proposed mechanism assumes the formation of a hypobromite in the rate-limiting step followed by a fast reaction to form products. The magnitude of the solvent isotope effect, $${{k'_{H_2 O} } \mathord{\left/{\vphantom {{k'_{H_2 O} } {k'_{D_2 O} }}} \right.\kern-\nulldelimiterspace} {k'_{D_2 O} }}$$is 0–90. The rates do not correlate satisfactorily with Taft’s substituent constants. An isokinetic relation is observed with β=331 K indicating enthalpy as a controlling factor.

    • Synthesis of cyano-bridged bimetallic complexes of η5-indenyl ruthenium(II): Characterization and spectroscopic studies

      K Mohan Rao E K Rymmai

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      Reactions of the cyanide complexes of the type [(Ind)Ru(PPh3)2CN] (1), [(Ind)Ru(dppe)CN] (2), [(Cp)Ru(PPh3)2CN] (3), with the corresponding chloro complexes [(Ind)Ru(PPh3)2Cl] (4), [(Ind)Ru(dppe)Cl] (5), [(Cp)Ru(PPh3)2Cl] (6), in the presence of NH4PF6 salt give homometallic cyano-bridged compounds of the type [(Ind)(PPh3)2Ru-CN-Ru(PPh3)2(Cp)]PF6 (7), [(Ind)(PPh3)2Ru-CN-Ru(PPh3)2(Ind)] PF6 where Ind = indenyl, η5-C9H7, (8), [(Cp)(PPh3)2Ru-CN-Ru(dppe)(Ind)]PF6, dppe = (Ph2PCH2CH2PPh2) (9), [(Ind(dppe)Ru-CN-Ru(PPh3)2(Ind)PF6 (10) and [(Ind)(dppe)Ru-CN-Ru(PPh3)2(Cp)]PF6 (11) respectively. Reaction of complex3 with [(p-cymene)RuCl2]2 dimer gave a mixed dimeric complex [(Cp)Ru(PPh3)2-CN-RuCl2(p-cymene)] (12). All these complexes have been characterized by IR,1H,13C and31P NMR spectroscopy and C, H, N analyses.

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