G R Dey
Articles written in Journal of Chemical Sciences
Volume 105 Issue 2 April 1993 pp 141-147 Physical and Theoretical
Volume 131 Issue 1 January 2019 Article ID 0001
The formation of radical cations and radicals of thioamides (R)(NH2)CS, where R represents CH3 in thioacetamide (TA) and C6H5 in thiobenzamide (TBA) in n-butyl chloride has been studied using pulse radiolysis technique. The radical cations of TA and TBA are observed in n-butyl chloride, and on their subsequentdeprotonation, respective radicals are generated. In this study on thioamide solutions in n-butyl chloride, the transient species formed at 1.2 μs after the electron pulse exhibiting absorption maxima in 400 nm region are attributed to their radical cations. In the presence of 0.1 M ethanol (C2H5OH), a radical cation scavenger, the absorbance values at corresponding peaks are reduced substantially, revealing the formation of their respective radical cations. Moreover, at a later time, the generation of radical species takes place through deprotonation of radical cations and also through direct reactions during electron pulse irradiation. The mechanisms for the formation of radical cations and radicals of these two thioamides under pulse radiolysis have been revisited inbutyl chloride medium wherein the charge transfer reactions are more prominent. Results of quantum chemical calculation support the mechanistic explanation and provide information on the reactivity of parent molecules, and the charge distribution on radical cations and radicals species of thioamides.
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