Kinetics and Mechanism of the Reaction of Dichlorotetraaquaruthenium(iii) and Thiols
Suprava Nayak A C , Gouri Sankhar Brahma B and K. Venugopal Reddy A
+ Author Affiliations
- Author Affiliations
A Department of Chemistry, Osmania University, Hyderabad-500 007, India.
B Faculty of Science and Technology, The ICFAI University, Dehradun-248197, India.
C Corresponding author. Email: suprava7107@gmail.com
Australian Journal of Chemistry 65(2) 113-120 https://doi.org/10.1071/CH11352
Submitted: 26 August 2011 Accepted: 18 October 2011 Published: 25 November 2011
Abstract
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.
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