Mechanistic Aspects of Ligand Substitution on the Cis-Diaqua-Chloro-Tris(Dimethyl Sulfoxide)Ruthenium(II) Complex by Some Sulfur-Containing Bioactive Ligands in Aqueous Medium

Author:

Chattopadhyay Animesh1,Dey Anwesha1,Karmakar Parnajyoti2,Ray Sumon1,Nandi Debabrata1,Sarkar(Sain) Roshni1,Ghosh Alak K1

Affiliation:

1. Department of Chemistry, The University of Burdwan, Burdwan 713104, West Bengal, India

2. Government General Degree College at Kalna-1, Muragacha, Medgachi, Burdwan-713405, West Bengal, India

Abstract

The synthesis and interactions of the cis-diaqua-chloro-tris(dimethyl sulfoxide)ruthenium(II) complex with selected sulfur-containing ligands such as 2-thiouracil, glutathione and L-cysteine have been studied by UV-Vis spectrophotometry in aqueous medium at pH 4.5. From experimental data it is clear that all three reactions proceed via two steps: the first one being a rate-limiting ligand-dependent replacement of one water molecule, followed by a ligand-independent ring closure step with the expulsion of the second water molecule. The substituted products have been characterised by Job's method, FTIR spectroscopy and electrospray ionisation mass spectrometry. Activation parameters (Δ H and Δ S) and thermodynamic parameters (Δ H0 and Δ S0, from the temperature dependence of the outer-sphere association equilibrium constant) are presented. Consistent with the experimental findings, an associative interchange mechanism is proposed.

Publisher

SAGE Publications

Subject

Physical and Theoretical Chemistry

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