Résumé
Local reactivity descriptors, such as atomic charges, atomic electrostatic potential andatomic Fukui indices were computed for a series of 3-substituted coumarin (2-oxo-2H-1-benzopyran)derivatives, using density functional theory (DFT) and Möller−Plesset methods (MP2). The variationof those properties as a function of the substituents was compared with the variation of the measuredXPS binding energies. The atomic electrostatic potentials and XPS binding energies serves as indicatorsof the electrophilicity of a given center within a molecule, while the atomic Fukui indices describe itsdegree of electronic localization, known as atomic softness. The correlation between those theoreticaland experimental properties allowed us to follow the effect of electron withdrawing substituents on theelectrophilicity of a given atomic center. The Fukui indices provided additional information about thesoftening/hardening of the center of interest due to presence of different substituents to the coumarin system. On the basis ofthese analysis, the 1,2-addition would be favored for 3-acetyl, 3-phosphono, and 7-diethylamino substituents, while 3-carboxyl, 3-ethoxycarbonyl, and 3-nitro substituent would favor 1,4-addition. The substituted coumarins would preferably react with softnucleophiles at position 2 and with hard nucleophiles at position 4.