Inorganic Chemistry

Aromatic, or Antiaromatic, That Is the Question:

Authors

Abstract

The term aromaticity in chemistry is reminiscent of symmetric, stable structures that have delocalized electrons and sustain diamagnetic ring currents in the presence of external magnetic fields. The two latter characteristics sometimes mistakenly are thought to be the same. In a groundbreaking discovery Liddle and co-workers synthesized a D3h complex with rare Th‒Th bonds. Studying the electronic structure of a neutral singlet model system, 3”, showed that the molecule has a delocalized HOMO between three Th atoms akin to a 2-electron 3-center bond. Employing nucleus independent chemical shift (NICS) computations and according to the pattern of the NICS scan plot on 3”, the authors suggested that the molecule is a σ-aromatic species as it is reflected also in the title of their paper. Unfortunately, NICS is an inappropriate tool for evaluation of the magnetic aromaticity among early and mid-transition metals (TM), the elements that share a characteristic with thorium; they all have low-energy unoccupied orbitals. In the following we explain why NICS fails to assess aromaticity of molecules containing TMs and prove that the Th3 ring is a weakly antiaromatic system. We introduce a simple protocol to examine the aromaticity of any molecule utilizing software packages, which have been used by the authors of the main article.

Content

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Supplementary material

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Supporting Information (1 Aromatic, or Antiaromatic, That Is the Question:)
The isosurfaces of current density at J(r) = 0.0003 au (Fig. S1), the profile and isosurface plots of the current density of benzene at different values (Fig. S2), and details of computational methods employed to perform the present work are presented in Supporting Information.