Issue 12, 2023

Thiol modifier effects of diphenyl diselenides: insight from experiment and DFT calculations

Abstract

A combination of spectroscopic, chromatographic and computational approaches was employed to investigate the reaction of several diselenides of formula (R-PhSe)2 (R = CH3O, CH3, H, Cl, CF3) with a thiolate nucleophile, leading to the breaking of the selenium–selenium (Se–Se) bond. This process has fundamental importance in biological environments and provides a rationale to analyze the so-called thiol modifier effect of diselenides, which may be exploited in pharmacology and toxicology. Our data suggest that withdrawing substituents favor the reaction, effectively making the reaction energy more negative, but strong electron-withdrawing groups also prompt structural modification on the starting reactant, increasing the reaction barrier. Thus, the nature (electron rich or electron poor) of the diselenides can play an essential role in the reactivity and biological activity of these molecules.

Graphical abstract: Thiol modifier effects of diphenyl diselenides: insight from experiment and DFT calculations

Supplementary files

Article information

Article type
Paper
Submitted
05 Dec. 2022
Accepted
12 Febr. 2023
First published
13 Febr. 2023
This article is Open Access
Creative Commons BY-NC license

New J. Chem., 2023,47, 5796-5803

Thiol modifier effects of diphenyl diselenides: insight from experiment and DFT calculations

P. A. Nogara, C. S. Oliveira, A. Madabeni, M. Bortoli, J. B. T. Rocha and L. Orian, New J. Chem., 2023, 47, 5796 DOI: 10.1039/D2NJ05976B

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