TY - JOUR
T1 - Oxidation of organic diselenides and ditellurides by H2O2 for bioinspired catalyst design
AU - Bortoli, Marco
AU - Zaccaria, Francesco
AU - Tiezza, Marco Dalla
AU - Bruschi, Matteo
AU - Guerra, Célia Fonseca
AU - Bickelhaupt, F. Matthias
AU - Orian, Laura
PY - 2018/7/24
Y1 - 2018/7/24
N2 - The reactivity of diselenides and ditellurides of general formula (RX)2 (X = Se, Te; R = H, CH3, Ph) toward hydrogen peroxide was studied through a computational approach based on accurate Density Functional Theory (DFT) calculations. The aliphatic and aromatic dichalcogenides have been chosen in light of their activity in glutathione peroxidase (GPx)-like catalytic cycles and their promising features as efficient antioxidant compounds. The reaction products, the energetics and the mechanistic details of these oxidations are discussed. Analogous disulfides are included in our analysis for completeness. We find that the barrier for oxidation of dichalcogenides decreases from disulfides to diselenides to ditellurides. On the other hand, variation of the substituents at the chalcogen nucleus has relatively little effect on the reactivity.
AB - The reactivity of diselenides and ditellurides of general formula (RX)2 (X = Se, Te; R = H, CH3, Ph) toward hydrogen peroxide was studied through a computational approach based on accurate Density Functional Theory (DFT) calculations. The aliphatic and aromatic dichalcogenides have been chosen in light of their activity in glutathione peroxidase (GPx)-like catalytic cycles and their promising features as efficient antioxidant compounds. The reaction products, the energetics and the mechanistic details of these oxidations are discussed. Analogous disulfides are included in our analysis for completeness. We find that the barrier for oxidation of dichalcogenides decreases from disulfides to diselenides to ditellurides. On the other hand, variation of the substituents at the chalcogen nucleus has relatively little effect on the reactivity.
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U2 - 10.1039/c8cp02748j
DO - 10.1039/c8cp02748j
M3 - Article
AN - SCOPUS:85051983091
VL - 20
SP - 20874
EP - 20885
JO - Physical Chemistry Chemical Physics
JF - Physical Chemistry Chemical Physics
SN - 1463-9076
IS - 32
ER -