The first nonconjugated mononuclear benzene dianion. Isolation and characterization of bis[(tetrahydrofuran)lithium(I)] hexakis(trimethylsilyl)benzenide

Sekiguchi, Akira; Ebata, Keisuke; Kabuto, Chizuko; Sakurai, Hideki

doi:10.1021/ja00004a086

Cited by 82 publications

(32 citation statements)

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“…There is a small arene distortion upon coordination, which is evidenced mainly in the lengthening of the arene CÀC bonds, with the coordinated C(53)ÀC(54) and C(51)ÀC(56) being the longest at 1.45 ( Figure 2). These structural data and the arene substitution chemistry outlined above for complexes 4 are more consistent with their formulation as Mo I 2 species with a coordinated neutral molecule of C 6 H 5 R rather than as Mo II 2 derivatives of an arene dianion, [36][37][38] C 6 H 5 R 2À . Thus, five pairs of d electrons would in principle be available for metal-metal bonding, as in the parent complex 3.…”

supporting

confidence: 75%

Interconversion of Quadruply and Quintuply Bonded Molybdenum Complexes by Reductive Elimination and Oxidative Addition of Dihydrogen

et al. 2013

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supporting

confidence: 75%

Interconversion of Quadruply and Quintuply Bonded Molybdenum Complexes by Reductive Elimination and Oxidative Addition of Dihydrogen

et al. 2013

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“…(f) The experimental structure of syn ‐[{Li(thf)} 2 (C 6 tms 6 )] has a compressed arene ring with a boat conformation D ,5 as predicted by our calculations on the unsubstituted benzene analogue, that is, syn ‐Li 2 (C 6 H 6 ).…”

Section: Introductionmentioning

confidence: 52%

“…Planar delocalized rings can also be found coordinated cofacially to two bonded molybdenum atoms as in 3 ,17, 25 and a delocalized puckered ring is also found in a syn conformation 4 in an Ni complex 30. In a lithium adduct of a benzene ring fully substituted with trimethylsilyl groups,5 the two lithium ions are cofacially arranged as in 5 , with two short and four long CC bonds, resulting in a boat conformation. However, when the steric hindrance in the hexasubstituted benzene is reduced by linking each pair of neighboring tms groups by CH 2 bridges, an anti conformation closer to 1 appears 13.…”

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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“…The only stable benzene-derived dianions known are highly conjugated [42][43] or sterically and electronically stabilized by multiple bulky silyl groups; [44][45][46] in the case of 1, the ability of the CAAC moieties to accept π-electron density from the ring leads to the stability of the highly reduced species 6.…”

Section: Figurementioning

confidence: 99%

Half-Sandwich Complexes of an Extremely Electron-Donating, Redox-Active η⁶-Diborabenzene Ligand

et al. 2018

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(4)). Investigation of the new complexes with a combination of X-ray diffraction, spectroscopic methods and DFT calculations shows that ligand 1 is a remarkably strong electron donor. In particular, [(η 6 -arene)M(CO) 3 ] complexes of this ligand display the lowest CO stretching frequencies yet observed for this class of complex. Cyclic voltammetry on complexes 2-4 revealed one reversible oxidation and two reversible reduction events in each case, with no evidence of ring-slippage of the arene to the η 4 binding mode. Treatment of 4 with lithium metal in THF led to identification of the paramagnetic complex [(1)W(CO) 3 ]Li·2THF (5). Compound 1 can also be reduced in the absence of a transition metal to its dianion 1 2-, which possesses a quinoid-type structure.

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The first nonconjugated mononuclear benzene dianion. Isolation and characterization of bis[(tetrahydrofuran)lithium(I)] hexakis(trimethylsilyl)benzenide

Cited by 82 publications

References 0 publications

Interconversion of Quadruply and Quintuply Bonded Molybdenum Complexes by Reductive Elimination and Oxidative Addition of Dihydrogen

Interconversion of Quadruply and Quintuply Bonded Molybdenum Complexes by Reductive Elimination and Oxidative Addition of Dihydrogen

Distortions of π‐Coordinated Arenes with Anionic Character

Half-Sandwich Complexes of an Extremely Electron-Donating, Redox-Active η⁶-Diborabenzene Ligand

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The first nonconjugated mononuclear benzene dianion. Isolation and characterization of bis[(tetrahydrofuran)lithium(I)] hexakis(trimethylsilyl)benzenide

Cited by 82 publications

References 0 publications

Interconversion of Quadruply and Quintuply Bonded Molybdenum Complexes by Reductive Elimination and Oxidative Addition of Dihydrogen

Interconversion of Quadruply and Quintuply Bonded Molybdenum Complexes by Reductive Elimination and Oxidative Addition of Dihydrogen

Distortions of π‐Coordinated Arenes with Anionic Character

Half-Sandwich Complexes of an Extremely Electron-Donating, Redox-Active η6-Diborabenzene Ligand

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Half-Sandwich Complexes of an Extremely Electron-Donating, Redox-Active η⁶-Diborabenzene Ligand