RESUMO

The electron delocalization of benzene (C6H6) and hexafluorobenzene (C6F6) was analyzed in terms of the induced magnetic field, nucleus-independent chemical shift (NICS), and ring current strength (RCS). The computed out-of-plane component of the induced magnetic field at a distance (r) greater than or equal to 1.0 Šabove the ring center correlates well (R (2)>0.99) with the RCS value. According to these criteria, fluorination has two effects on the C6 skeleton; concomitantly, the resonant effects diminish the π electron delocalization and the inductive effects decrease the charge density at the ring center and therefore reduce the magnitude of the paratropic current generated in this region. The equilibrium between both effects decreases aromaticity in the fluorinated benzene derivatives. These results can be extrapolated to determine the aromaticity of any derivative within the series of fluorinated benzene derivatives (C6H(6-n)F n , where n=1-5).

RESUMO

The potential energy surfaces (PESs) of Lin(BH)5(n-6) systems (where n = 5, 6, and 7) were explored using the gradient embedded genetic algorithm (GEGA) program, in order to find their global minima conformations. This search predicts that the lowest-energy isomers of Li6(BH)5 and Li7(BH)5(+) contain a (BH)5(6-) pentagonal fragment, which is isoelectronic and structurally analogous to the prototypical aromatic hydrocarbon anion C5H5(-). Li7(BH)5(+), along with Li7C5(+), Li7Si5(+) and Li7Ge5(+), joins a select group of clusters that adopt a seven-peak star-shape geometry, which is favored by aromaticity in the central five-membered ring, and by the preference of Li atoms for bridging positions. The theoretical analysis of chemical bonding, based on magnetic criteria, supports the notion that electronic delocalization is an important stabilization factor in all these star-shaped clusters.

Assuntos

RESUMO

Although aromaticity is a concept in chemistry, in the last years, special efforts have been carried out in order to propose theoretical strategies to quantify it as a property of molecular rings. Among them, perhaps the computation of nucleus independent chemical shifts (NICSs) is the most commonly used, since it is possible to calculate it in an easy and fast way with most used quantum chemistry software. However, contradicting assignments of aromaticity by NICS and other methods have been reported in the literature, especially in studies concerning inorganic chemistry. In this Article is proposed a new and simple strategy to use the NICS information to assess aromaticity, identifying the point along the axis perpendicular to the molecular plane where the in-plane component of NICS becomes zero; it is called free of in-plane component NICS (FiPC-NICS). This spatial point is proposed as secure to consider NICS as an aromaticity descriptor; this simple proposal is evaluated in borazine and cyclotriphosphazenes. The results are compared with carefully examined aromatic stabilization energies and magnetically induced current-density analysis.

Assuntos

RESUMO

A recently proposed molecular orbital localization procedure, based on the electron localization function (ELF) technique, has been used to describe chemical bonding in the cluster series Sin(BH)(5-n)(2-) (n = 0-5). The method combines the chemically intuitive information obtained from the traditional ELF analysis with the flexibility and generality of canonical molecular orbital theory. This procedure attempts to localize the molecular orbitals in regions that have the highest probability for finding a pair of electrons, providing a chemical bonding description according to the classical Lewis theory. The results confirm that conservation of the structures upon isoelectronic replacement of a B-H group by a Si atom, allowing evolution from B5H5(2-) to Si5(2-), is in total agreement with the preservation of the chemical bonding pattern.