A theoretical analysis of atomic charge fluxes in chlorofluoromethanes and relationship with bonding character descriptors

Abstract

Atomic substitutions in chlorofluoromethanes were analyzed through changes in the bond character descriptors and the related effect on electronic charge fluxes, given by the QTAIM model, which occur during atomic stretching displacements. Such interpretation of halogenation may provide new insights on reaction coordinate and halogen-bonding studies.

A Quantum Theory Atoms in Molecules Study about the Inductive Effect of Substituents in Methane Derivatives

“…Figure 4 Finally, we examined the relationship between the electric field at the carbon nucleus due to substituent charges, which was determined along the C−H line toward hydrogen, and the local descriptors of the covalent character studied. A nonlinear correlation curve seems to be observed, supporting the idea proposed in our previous study, 10 that is, the inductive effect is due to polarizations caused by the partial charges of substituents. Therefore, the inductive effect propagates through space (field effect), but the transmission depends on the presence of chemical bonds along the path, which will be polarized by the field.…”

“…Here, we decided to extend the aforementioned study of inductive effects on the covalent character of C–H bonds in methane derivatives by considering several substituents (−CH 3 , −F, −Cl, −Br, −OH, −SH, O, S, −NO 2 , −NH 2 , −OCH 3 , −Li, and −Na) and also examining a semiquantitative descriptor that reinforces the explanation previously proposed in terms of polarization due to the atomic charges of substituents.…”

“…Our research group also used QTAIM to evaluate the inductive effects of substituents on the covalent character of C−H, C−F, and C−Cl bonds in small organic compounds (methane, fluoro-, chloro-and chlorofluoromethanes). 10 Therefore, the presence of halogens increased the covalent character of these bonds, and an explanation was proposed in terms of polarization effects due to the partial atomic charges of these substituents in such molecules.…”

“…They discussed that the inductive effect propagates via atomic dipole moment manipulation, which is consistent with the field mechanism, but is propagated along bond paths, in agreement with the traditional inductive effect definition. Our research group also used QTAIM to evaluate the inductive effects of substituents on the covalent character of C–H, C–F, and C–Cl bonds in small organic compounds (methane, fluoro-, chloro- and chlorofluoromethanes) . Therefore, the presence of halogens increased the covalent character of these bonds, and an explanation was proposed in terms of polarization effects due to the partial atomic charges of these substituents in such molecules.…”