Dipositive ion of hexachlorobenzene. Ground-state triplet

Wasserman, E.; Hutton, R. S.; Kuck, Valerie J.; Chandross, Edwin A.

doi:10.1021/ja00813a068

Cited by 62 publications

(26 citation statements)

References 1 publication

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“…However, triplet ground states have been predicted for these dications, and accordingly, their isolation as stable entities in the condensed phase should be relatively difficult ( Fig. 1c) [31][32][33] . The two-electron oxidation of hexakis(dimethylamino)benzene (5) afforded the corresponding dication, which revealed a alternation of the C−C bonds in the central benzene ring 34 , indicative of a considerable contribution from a quinoidal resonance structure, which indicates the absence of double aromaticity.…”

Section: Resultsmentioning

confidence: 99%

Double aromaticity arising from σ- and π-rings

et al. 2018

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Aromaticity has been a central concept in chemistry since the discovery of benzene in the 19th century and has impacted the science of delocalized π-electron systems. The aromaticity of conventional aromatic compounds usually originates from electron delocalization through a single ring that consists of π-symmetric orbitals. Although double aromaticity, i.e. aromaticity composed of two circularly delocalized orbitals, has been theoretically predicted for over 20 years, the double aromaticity of a bench-stable compound is not well explored by experiment. Here we report the synthesis and isolation of the dication of hexakis (phenylselenyl)benzene, as well as its double aromaticity based on structural, energetic, and magnetic criteria. In this dication, cyclic σ-symmetric and π-symmetric delocalized orbitals are formally occupied by ten and six electrons, respectively, and the aromaticity thus follows the 4n + 2 (n = 1, 2,…) electron Hückel rule, regardless of the σ-orbital or π-orbital symmetry.

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Section: Resultsmentioning

confidence: 99%

Double aromaticity arising from σ- and π-rings

et al. 2018

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“…Oxidation of hexaiodobenzene (C 6 I 6 ) with Cl 2 or H 2 O 2 yielded a stable salt without any electron spin resonance (ESR) signal suggesting that a C 6 I 2+ 6 dication with a singlet ground state was obtained in the synthesis, 1 whereas similar experiments on C 6 Cl 6 yielded a C 6 Cl 2+ 6 dication in the triplet state as judged from ESR measurements. 1,2 The closed-shell C 6 I 2+ 6 dication was found to exhibit σ delocalisation between the iodine atoms. 1 A milder oxidation of C 6 I 6 using SbF 5 or AsF 5 yielded a salt containing the C 6 I + 6 radical dication, which has as C 6 I 2+…”

Section: Introductionmentioning

confidence: 98%

Calculations of current densities for neutral and doubly charged persubstituted benzenes using effective core potentials

Rauhalahti

Taubert

Sundholm

et al. 2017

Phys. Chem. Chem. Phys.

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Magnetically induced current density susceptibilities and ring-current strengths have been calculated for neutral and doubly charged persubstituted benzenes CX and CX with X = F, Cl, Br, I, At, SeH, SeMe, TeH, TeMe, and SbH. The current densities have been calculated using the gauge-including magnetically induced current (GIMIC) method, which has been interfaced to the Gaussian electronic structure code rendering current density calculations using effective core potentials (ECP) feasible. Relativistic effects on the ring-current strengths have been assessed by employing ECP calculations of the current densities. Comparison of the ring-current strengths obtained in calculations on CAt and CAt using relativistic and non-relativistic ECPs show that scalar relativistic effects have only a small influence on the ring-current strengths. Comparisons of the ring-current strengths and ring-current profiles show that the CI, CAt, C(SeH), C(SeMe), C(TeH), C(TeMe), and C(SbH) dications are doubly aromatic sustaining spatially separated ring currents in the carbon ring and in the exterior of the molecule. The CI radical cation is also found to be doubly aromatic with a weaker ring current than obtained for the dication.

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“…With two electrons in the same HOMO we can give a minimum description for D n h symmetry resulting into a low‐lying antisymmetric singlet state Ψ 4 and a higher symmetric singlet state Ψ 5 : This combination results in a negligible energy difference between the triplet and singlet state of n = 4,8 ‐ ‐ ‐ and −2 K μν in favor of the triplet state of n = 3,5,‐ ‐ ‐ or n = 6,10, ‐ ‐ ‐. The existence of a triplet state has been established for the cyclopentadienyl cation 26 and the dication of hexachlorobenzene 27.…”

Section: Results Of the Calculationsmentioning

confidence: 95%

Quantum chemical study of alternating N/B and N/C π bonds in (un)charged even‐membered 4n and 4n+2 cyclic systems and their related open systems

Buck¹

2004

Int J of Quantum Chemistry

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ABSTRACT:With semi-empirical MO and ab initio calculations at different levels, we investigated the conjugation of alternating XOY bonds with XOY for N/B and N/C combinations in an open and cyclic arrangement. Although the intrinsic symmetry is lost for the acyclic even-membered compounds, the alternation is still reflected in its geometry and electron-density transfer. For the cyclic compounds, we focused our attention on borazine N 3 B 3 H 6 (D 3h symmetry), which is isoelectronic with benzene (D 6h symmetry). Specific attention is given to the electrophilic behavior of borazine with respect to CH 3 ϩ and SiMe 3 ϩ . The dynamics based on the results of FT-ICR mass spectrometry was studied in more detail. In addition, the results of the cyclic systems with 4n and 4nϩ2 electrons concerning their geometries are compared with the corresponding carbon compounds. Attention is also given to the dication of borazine, because of the corresponding triplet ground state of the benzene dication.

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Dipositive ion of hexachlorobenzene. Ground-state triplet

Cited by 62 publications

References 1 publication

Double aromaticity arising from σ- and π-rings

Double aromaticity arising from σ- and π-rings

Calculations of current densities for neutral and doubly charged persubstituted benzenes using effective core potentials

Quantum chemical study of alternating N/B and N/C π bonds in (un)charged even‐membered 4n and 4n+2 cyclic systems and their related open systems

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