Suprava Nayak

Kinetics and Mechanism of the Reaction of Dichlorotetraaquaruthenium(III) and Thiols

The formation of an intermediate ruthenium(iii) thiolate complex by the interaction of thiols, RSH (R = glutathione and l-cysteine) and dichlorotetraaquaruthenium(iii), [RuIIICl2(H2O)4]+, is reported in the temperature range 25–40°C. The kinetics and mechanism of formation of the intermediate complex were studied as a function of [RuIIICl2(H2O)4]+, [RSH], pH, ionic strength and temperature. Reduction of the intermediate complex takes place slowly and results in the corresponding disulfides RSSR and [RuIICl2(H2O)4]+. The results are interpreted in terms of a mechanism involving a rate-determining inner-sphere one-electron transfer from RSH to the oxidant used in the present investigation and a comparison of rate and equilibrium constants is presented with activation parameters.

Kinetics and mechanism of the reactions of hexaaqua rhodium (III) with sulphur (IV) in aqueous medium

An O-bonded sulphito complex, Rh(OH2)5(OSO2H)2+, is reversibly formed in the stoppedflow time scale when Rh(OH2)63+ and SO2/HSO3− buffer (1 <pH< 3) are allowed to react. For Rh(OH2)5OH2++ SO2 □ Rh(OH2)5(OSO2H)2+ (k1/k-1), k1 = (2.2 ±0.2) × 103 dm3 mol−1 s−1, k−1 = 0.58 ±0.16 s−1 (25°C,I = 0.5 mol dm−3). The protonated O-sulphito complex is a moderate acid (Kd = 3 × 10−4 mol dm−3, 25°C, I= 0.5 mol dm−3). This complex undergoes (O, O) chelation by the bound bisulphite withk= 1.4 × 10−3 s−1 (31°C) to Rh(OH2)4(O2SO)+ and the chelated sulphito complex takes up another HSO3− in a fast equilibrium step to yield Rh(OH2)3(O2SO)(OSO2H) which further undergoes intramolecular ligand isomerisation to the S-bonded sulphito complex: Rh(OH2)3(O2SO)(OSO2)- → Rh(OH2)3(O2SO)(SO3)− (kiso = 3 × 10−4 s−1, 31°C). A dinuclear (μ-O, O) sulphite-bridged complex, Na4[Rh2(μ-OH)2(OH)2(μ-OS(O)O)(O2SO)(SO3) (OH2)]5H2O with (O, O) chelated and S-bonded sulphites has been isolated and characterized. This complex is sparingly soluble in water and most organic solvents and very stable to acid-catalysed decomposition