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Vol. 35 No. 4 (2023): Vol 35 Issue 4, 2023

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Copper(II) Catalyzed Oxidation of Aliphatic Thiols (Thioglycolic Acid and 2-Mercaptoethanol) by Heteroleptic Co(III)-Bound Superoxo Complex

https://doi.org/10.14233/ajchem.2023.27587
A. Mandal
Department of Chemistry, Bidhannagar College, Kolkata-700064, India
https://orcid.org/0009-0008-4365-8749

Corresponding Author(s) : A. Mandal

arabindaju@rediffmail.com

Asian Journal of Chemistry, Vol. 35 No. 4 (2023): Vol 35 Issue 4, 2023

Abstract

In aqueous acid media (0.02-0.06 M), two aliphatic thiols (RSH) viz. thioglycolic acid (TGA) and mercapto ethanol (MERCAP) were oxidized by heteroleptic metal bound superoxo complex, [(dien)(en)CoIII(O2)CoIII(en)(dien)]5+ (1) (en = ethylenediamine, NH2CH2CH2NH2 and dien = diethylenetriamime, NH2(CH2)2NH(CH2)2NH2) to the corresponding disulphides. Complex 1 is reduced to its corresponding peroxo complex, [(dien)(en)CoIII(O2)CoIII(en)(dien)]4+ (2) in these reactions. The oxidation of both thiols were dramatically catalyzed by the presence of Cu2+ ion. The observed rate constant ko was found to be proportional to [RSH]2 and [Cu]T2 (where [Cu]T is the analytical concentration of Cu2+). The rate of reaction decreases with increasing ionic strength (I) of the reaction media and ko is also proportional to [H+]2–. The experimental observation suggests that a 1:2 anionic complex formed between Cu2+ and RSH participates in the redox cycle.

Keywords

Thiols Thioglycolic acid Mercapto ethanol Superoxide Redox reaction Kinetics
Mandal, A. (2023). Copper(II) Catalyzed Oxidation of Aliphatic Thiols (Thioglycolic Acid and 2-Mercaptoethanol) by Heteroleptic Co(III)-Bound Superoxo Complex. Asian Journal of Chemistry, 35(4), 969–976. https://doi.org/10.14233/ajchem.2023.27587
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