1,2‐Diphenylbenzene Dianion: Alkali‐Metal Salts with Drastically Spread C<sub>6</sub> Rings

“… 12 Considering a broad family of polycyclic hydrocarbons, monoanion-radicals are well-documented and have been characterized both in solution and solid state for a great number of polyaromatic scaffolds. 13 , 14 In contrast, the number of isolated and structurally characterized trianion-radicals is limited. Only for C 60 -fullerene, the trianions are well-known, 15 stemming from the triply degenerate nature of its low-lying unoccupied molecular orbital (LUMO) that can accept up to six electrons.…”

Section: Introductionmentioning

confidence: 99%

Supramolecular trap for a transient corannulene trianion

et al. 2016

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“…Its iconic character brings to mind crucial steps in the development of modern concepts of molecular structure and bonding, from Kekulé1 to Pauling 2. The phenyl group can undergo one‐ and two‐electron reductions, and salts of the corresponding benzenide mono‐3 and dianions4–6 have been characterized. A tetraanionic form of arene rings has also been reported to be stabilized by calcium in the unusual oxidation state Ca I 7.…”

Section: Introductionmentioning

confidence: 99%

Distortions of π‐Coordinated Arenes with Anionic Character

Falceto

Casanova

Alemany

et al. 2014

Chemistry A European J

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A qualitative analysis of the distortions that operate on the π system of bridging arenes with anionic character is presented and substantiated by computational studies at the density functional B3LYP and CASSCF levels. The observed effects of bonding to two metal atoms and of the negative charge are an expansion of the arene ring due to the partial occupation of π* orbitals, an elongation or compression distortion accompanied by a loss of the equivalence of carbon-carbon bonds due to a Jahn-Teller distortion of the arene dianions, and a ring puckering due to a second-order Jahn-Teller distortion that may appear independently of the existence of the first-order effect. The workings of the orbital mixing produced by these distortions have been revealed in a straightforward way by a pseudosymmetry analysis of the HOMOs of the distorted conformations. The systems studied include Li(I) and Y(III) adducts of benzene, as well as trimethylsilyl-substituted derivatives in the former case. An analysis of the structural data of a variety of purported di- and tetraanionic arene ligands coordinated to transition metals in several bridging modes has reproduced the main geometrical trends found in the computational study for the benzene and trimethylsilyl-substituted benzene dianions, allowing a classification of the variety of structural motifs found in the literature.

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1,2‐Diphenylbenzene Dianion: Alkali‐Metal Salts with Drastically Spread C₆ Rings

Cited by 25 publications

References 20 publications

Heterobimetallic Pd–K carbene complexes via one-electron reductions of palladium radical carbenes

Heterobimetallic Pd–K carbene complexes via one-electron reductions of palladium radical carbenes

Supramolecular trap for a transient corannulene trianion

Distortions of π‐Coordinated Arenes with Anionic Character

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1,2‐Diphenylbenzene Dianion: Alkali‐Metal Salts with Drastically Spread C6 Rings

Cited by 25 publications

References 20 publications

Heterobimetallic Pd–K carbene complexes via one-electron reductions of palladium radical carbenes

Heterobimetallic Pd–K carbene complexes via one-electron reductions of palladium radical carbenes

Supramolecular trap for a transient corannulene trianion

Distortions of π‐Coordinated Arenes with Anionic Character

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Product

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1,2‐Diphenylbenzene Dianion: Alkali‐Metal Salts with Drastically Spread C₆ Rings