Open AccessN-t-Butyl-α-aryl Nitrones as Potent Spin Traps: DFT Analysis of Electron Localization Function Topology, Local Selectivity, Reactivity and Solvent Effects
Author(s) -
Nivedita Acharjee,
Sourav Mondal
Publication year - 2020
Publication title -
asian journal of chemistry/asian journal of chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.145
H-Index - 34
eISSN - 0975-427X
pISSN - 0970-7077
DOI - 10.14233/ajchem.2020.22590
Subject(s) - chemistry , hydroperoxyl , reactivity (psychology) , aryl , nucleophile , electrophile , adduct , density functional theory , nitrone , radical , computational chemistry , medicinal chemistry , photochemistry , organic chemistry , alkyl , medicine , alternative medicine , pathology , cycloaddition , catalysis
Density functional theory studies were performed to analyze the reactivity and selectivity of radicalcapture by N-t-butyl-α-aryl nitrones. Biologically relevant three important radicals viz. hydroxyl, methyland hydroperoxyl were selected for the study. Topological analysis of the electron localization function(ELF) allows to classify these nitrones as zwitter-ionic type three atom components (TAC). Effects ofelectron withdrawing and electron donating C-aryl substituents on the electronic chemical potentials,global hardness, electrophilic and nucleophilic indices of nitrones were observed. Radical attack atthe carbon atom was predicted by Merz-Kollman algorithm, which is in agreement with the experimentsunlike the natural population analysis. Hydroxyl adducts were predicted to be more stable than methyland hydroperoxyl adducts. cis-Adducts were more stable than the trans-, with the highest differencesin stability noted for the methyl adducts. Relative energies of adducts was lowered in non-polar solventsand thus increase in stability was observed along the series from water to heptane.