Effects of the charge on the structural, electronic and reactivity properties of 43 substituted N–Phenylmaleimides. A DFT study

• Geometrical and electronic properties of N-phenylmaleimide compounds.
• Charge transfer effects on the reactivity properties of N-phenylmaleimides.
• Importance of the phenyl-maleimide torsion angle on the reactivity properties of these compounds.
• Use of density functional theory based methods for the study of the electronic and energetic parameters of N-phenylmaleimides.

The structural, electronic, and reactivity properties of 43 N-phenylmaleimide derivatives were studied by means of first principles theoretical calculations performed at the B3LYP/6-311+G(d,p) level of theory. Neutral, positively and negatively charged derivatives were studied. Different donor- and attractor-electron groups, attached at the ortho, meta and para positions, were selected, allowing to search for the effects of the charge on the geometrical, energetic and reactivity properties of the generated compounds. Firstly, the calculated ground state (GS) structures are in near agreement with the reported experimental X-Ray data and provide insight on some main features of the observed infrared spectra. Besides, the GS geometries show that the torsion angle, of the phenyl–maleimide rings, is an important parameter that impacts the properties of the species and of the polymeric chains, formed from such N-phenylmaleimides. It was found that the torsion angles depends on the nature (donor or attractor) of the selected group, on the position (ortho, meta, or para) on which the substitution was done, and on the charge (0e, +1e, −1e). For each compound, the effects of the charge on the: torsion angles, electronic (atomic populations and molecular orbitals) and energetic parameters (ionization energies and electron affinities) were studied. This information allows determining the chemical potentials, hardness, softness as well as the Fukui functions. Thus, the reactivity properties of these compounds were determined at this level of treatment. In neutral N-phenylmaleimides, the electrophylic attack mainly proceeds via the phenyl ring whereas the nucleophylic behavior is mostly defined by the imide group. These behaviors are enhanced on the cation and anion, respectively. Changes of these properties, produced by the substituent groups, are addressed.

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