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Kinetics and mechanism of biphasic substitution reactions of a platinum(II) complex with thioglycollic acid and 4-methyl-3-thiosemicarbazide in aqueous solution

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Abstract

The kinetics of interactions between cis-diaqua(2-aminomethylpyridine)platinum(II) perchlorate (1) [Pt(pic)(OH2)2](ClO4)2, thioglycollic acid (TGA), and 4-methyl-3-thiosemicarbazide (MTSC) have been studied spectrophotometrically in aqueous medium as a function of the [complex (1)] as well as [TGA] or [MTSC], pH and temperature at constant ionic strength. The observed pseudo-first-order rate constants were proportional to [TGA] or [MTSC]. At pH 4.0, the interactions of (1) with both TGA and MTSC show two distinct consecutive steps; the first step is dependent and second independent of [TGA] or [MTSC]. The association equilibrium constant (K E) for the outer sphere complex formation has been evaluated, along with the rate constants for the two steps. The first step is assigned to ligand-assisted anation and the second to chelation of TGA or MTSC. The activation parameters for both the steps were evaluated using Eyring’s equation. On the basis of the kinetic observations and evaluated activation parameters, an associative mechanism is proposed for both the reactions.

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Acknowledgment

The authors KM and SCM are thankful to National Institute of Technology Durgapur-713209 and Government of India for providing financial assistance from DST Project Fund (Project NO.: SB/EMEQ-028/2013) and necessary assistance for carrying out this work. Thanks to reviewer for his valuable suggestions.

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Authors and Affiliations

  1. Department of Chemistry, National Institute of Technology, Durgapur, 713209, W.B., India

    Koyel Misra, Ishani Mitra, Goutam Kr. Ghosh, Subhajit Mukherjee & Sankar Ch. Moi

  2. Institute of Applied Synthetic Chemistry, Vienna University of Technology, Getreidemarkt, 9/163-AC, 1060, Vienna, Austria

    Bashkim Misini & Wolfgang Linert

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  1. Koyel Misra
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  2. Ishani Mitra
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  3. Goutam Kr. Ghosh
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  4. Subhajit Mukherjee
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  5. Bashkim Misini
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  6. Wolfgang Linert
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  7. Sankar Ch. Moi
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Correspondence to Sankar Ch. Moi.

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Misra, K., Mitra, I., Ghosh, G.K. et al. Kinetics and mechanism of biphasic substitution reactions of a platinum(II) complex with thioglycollic acid and 4-methyl-3-thiosemicarbazide in aqueous solution. Transition Met Chem 39, 789–796 (2014). https://doi.org/10.1007/s11243-014-9861-6

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