Search

The review summarizes the results of previous and the latest studies on aromaticity and related concepts. The electron counting rule for 3D-aromatic systems 2(n + 1)2 is shown to be a generalization of the 4n + 2 rule for planar molecules, and, vice versa, the latter can be derived from the former. The relative stability of the push–pull and captodative aromatic systems is shown to depend on the nature of the groups separated by the C=C bond in geminal or vicinal positions. The fully symmetrical molecules of hexamethylbenzene and hexacyanobenzene were studied using structural, energetic, and NMR criteria, and the donor substituents were shown to increase the aromaticity. Taking into account the coincidence of the number of π-electrons in aromatic systems with the number of electrons on the filled electron subshells (s, p, d, and f) and considering electrons as objects in a space of states allowed to conclude that no g-elements can exist and that the extension of the Periodic Table is possible only by filling 6f, 7d, or 8s subshells. The dimensionality of space also affects the chirality of molecules, making planar or even linear molecules chiral on oriented surfaces, which can be used for the preparation of enantiomerically pure drugs, resolution of prochiral compounds, etc. [ABSTRACT FROM AUTHOR]

The review summarizes the results of previous and the latest studies on aromaticity and related concepts. The electron counting rule for 3D-aromatic systems 2(n + 1)2 is shown to be a generalization of the 4n + 2 rule for planar molecules, and, vice versa, the latter can be derived from the former. The relative stability of the push–pull and captodative aromatic systems is shown to depend on the nature of the groups separated by the C=C bond in geminal or vicinal positions. The fully symmetrical molecules of hexamethylbenzene and hexacyanobenzene were studied using structural, energetic, and NMR criteria, and the donor substituents were shown to increase the aromaticity. Taking into account the coincidence of the number of π-electrons in aromatic systems with the number of electrons on the filled electron subshells (s, p, d, and f) and considering electrons as objects in a space of states allowed to conclude that no g-elements can exist and that the extension of the Periodic Table is possible only by filling 6f, 7d, or 8s subshells. The dimensionality of space also affects the chirality of molecules, making planar or even linear molecules chiral on oriented surfaces, which can be used for the preparation of enantiomerically pure drugs, resolution of prochiral compounds, etc.

To describe aromaticity of planar and three‐dimensional molecules, different electron counting rules are employed. Here, the relationship between the Hückel 4n + 2 rule and the Hirsch 2(n + 1)2 rule is established based on formal approach considering the electrons as objects in an arbitrary n‐dimensional space of states. Two types of three‐dimensional aromaticity, referred to as 'spherical' (following the 4n + 2 electron counting rule) and 'spatial' (following the 2(n + 1)2 electron counting rule) are distinguished. A conclusion concerning the boundaries of the Periodic Table of Elements is made based on the same formal approach that no g‐ (or higher) elements can exist and that possible extension of the Periodic Table beyond the seventh period must be followed by filling of the 8p or inner 6f or 7d levels. Copyright © 2011 John Wiley & Sons, Ltd. [ABSTRACT FROM AUTHOR]