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Single─Not Double─3D-Aromaticity in an Oxidized Closo Icosahedral Dodecaiodo-Dodecaborate Cluster

Authors: Jordi Poater; Sílvia Escayola; Albert Poater; Francesc Teixidor; Henrik Ottosson; Clara Viñas; Miquel Solà;

Single─Not Double─3D-Aromaticity in an Oxidized Closo Icosahedral Dodecaiodo-Dodecaborate Cluster

Abstract

3D-aromatic molecules with (distorted) tetrahedral, octahedral, or spherical structures are much less common than typical 2D-aromatic species or even 2D-aromatic-in-3D systems. Closo boranes, [BnHn]2- (5 ≤ n ≤ 14) and carboranes are examples of compounds that are singly 3D-aromatic, and we now explore if there are species that are doubly 3D-aromatic. The most widely known example of a species with double 2D-aromaticity is the hexaiodobenzene dication, [C6I6]2+. This species shows π-aromaticity in the benzene ring and σ-aromaticity in the outer ring formed by the iodine substituents. Inspired by the hexaiodobenzene dication example, in this work, we explore the potential for double 3D-aromaticity in [B12I12]0/2+. Our results based on magnetic and electronic descriptors of aromaticity together with 11B{1H} NMR experimental spectra of boron-iodinated o-carboranes suggest that these two oxidized forms of a closo icosahedral dodecaiodo-dodecaborate cluster, [B12I12] and [B12I12]2+, behave as doubly 3D-aromatic compounds. However, an evaluation of the energetic contribution of the potential double 3D-aromaticity through homodesmotic reactions shows that delocalization in the I12 shell, in contrast to the 10σ-electron I62+ ring in the hexaiodobenzene dication, does not contribute to any stabilization of the system. Therefore, the [B12I12]0/2+ species cannot be considered as doubly 3D-aromatic.

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Sweden, Spain, Spain
Keywords

Fysikalisk kemi, Organisk kemi, Aromatic compounds, Organic Chemistry, Physical Chemistry, Aromaticity (Chemistry), B-11 NMR spectra, Independent chemical-shifts, Compostos aromàtics, Electron delocalization, Aromaticitat (Química), Substitute benzene dications

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selected citations
These citations are derived from selected sources.
This is an alternative to the "Influence" indicator, which also reflects the overall/total impact of an article in the research community at large, based on the underlying citation network (diachronically).
BIP!Citations provided by BIP!
popularity
This indicator reflects the "current" impact/attention (the "hype") of an article in the research community at large, based on the underlying citation network.
BIP!Popularity provided by BIP!
influence
This indicator reflects the overall/total impact of an article in the research community at large, based on the underlying citation network (diachronically).
BIP!Influence provided by BIP!
impulse
This indicator reflects the initial momentum of an article directly after its publication, based on the underlying citation network.
BIP!Impulse provided by BIP!
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