An Isolable Bismabenzene: Synthesis, Structure, and Reactivity

Ishii, Takuya; Suzuki, Katsunori; Nakamura, Takashi; Yamashita, Makoto

doi:10.1021/jacs.6b08714

Cited by 42 publications

(37 citation statements)

References 38 publications

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…Another strategy is to introduce a heteroatom into the π-conjugated core, for which we choose silicon (Z in Scheme 1) as sila-aromatics have been shown to be realistic synthetic targets. [58][59][60][61][62][63][64] Our analyses reveal two electronic mechanisms at work that are responsible for the decrease of ΔE frag H-L upon introducing Si into the benzene core ( Fig. 3c).…”

Section: Heteroatom Substitution In Aromatic Corementioning

confidence: 99%

Rational design of near‐infrared absorbing organic dyes: Controlling the HOMO–LUMO gap using quantitative molecular orbital theory

et al. 2018

View full text Add to dashboard Cite

Principles are presented for the design of functional near‐infrared (NIR) organic dye molecules composed of simple donor (D), spacer (π), and acceptor (A) building blocks in a D‐π‐A fashion. Quantitative Kohn–Sham molecular orbital analysis enables accurate fine‐tuning of the electronic properties of the π‐conjugated aromatic cores by effecting their size, including silaaromatics, adding donor and acceptor substituents, and manipulating the D‐π‐A torsional angle. The trends in HOMO–LUMO gaps of the model dyes correlate with the excitation energies computed with time‐dependent density functional theory at CAMY‐B3LYP. Design principles could be developed from these analyses, which led to a proof‐of‐concept linear D‐π‐A with a strong excited‐state intramolecular charge transfer and a NIR absorption at 879 nm. © 2018 The Authors. Journal of Computational Chemistry published by Wiley Periodicals, Inc.

show abstract

Section: Heteroatom Substitution In Aromatic Corementioning

confidence: 99%

Rational design of near‐infrared absorbing organic dyes: Controlling the HOMO–LUMO gap using quantitative molecular orbital theory

et al. 2018

View full text Add to dashboard Cite

show abstract

“…Benzene and the concept of aromaticity is central to chemistry . Generations of researchers have undertaken significant efforts to extend this concept to other elements than carbon . Naturally, a particular focus has been on the heavier members of group 14 in particular silicon and germanium .…”

Section: Introductionmentioning

confidence: 99%

A One‐Step Germole to Silole Transformation and a Stable Isomer of a Disilabenzene

Reinhold

Dong

Winkler

et al. 2017

Chemistry A European J

View full text Add to dashboard Cite

An unusual germole-to-silole transformation is described. As key intermediates hetero-fulvenes are formed which rearrange to more stable bicyclic carbene analogues. The so-formed germylenes undergo a reductive elimination yielding elemental germanium and siloles. In contrast, the analogous silylenes are stable at ambient conditions and were identified by MS spectrometry and NMR spectroscopy supported by the results of quantum mechanical calculations. These bicyclic silylenes are stable derivatives of the global minimum of the C Si H potential energy surface.

show abstract

“…Although phosphorus analogues, that is, phosphacyclohexadienes, are known, a similar structural fragment is very rare for the bismuth atom. We are aware of only one structurally authenticated example, recently reported by Suzuki (Figure D). Its main structural data and boat conformation are consistent with the structure of 10 .…”

Section: Resultsmentioning

confidence: 93%

“…Very recently, Suzuki et al. reported on a bisma‐DA reaction between a sterically protected bismabenzene and dimethyl acetylenedicarboxylate (DMAD), which afforded the corresponding bisma[2.2.2]bicyclooctadiene in essentially quantitative yield (Scheme A) …”

Section: Introductionmentioning

confidence: 99%

Hetero Diels–Alder Reactions of Masked Dienes Containing Heavy Group 15 Elements

Kořenková

Kremláček

Hejda

et al. 2020

Chemistry A European J

View full text Add to dashboard Cite

Treatment of N,C,N-chelated organopnictogen(I) compounds ArE (1-3)( Ar = 2,6-(RN=CH) 2 C 6 H 3 ,E /R = As/Dmp (1), Sb/tBu (2), and Bi/tBu (3), where Dmp = 2,6-Me 2 C 6 H 3 ) with various electron-deficient alkynes RCCR' (R/R' = CO 2 Me (DMAD), R/R' = H/CO 2 Me, or R/R' = NC 5 F 4 )a ffords different types of heterocyclic compounds. In these reactions, 1-3 act as hidden dienes and participate in hetero-Diels-Alder (DA) reactions, af eature that has been only rarely reported for heavierp nictogen compounds. In this way,r eactions of 1 furnished the set of 1-arsanaphthalenes 4-6.T he mostl ikely mechanism involves two steps, that is, an arsa-DA reaction giving a1 -arsa-1,4-dihydro-iminonaphthalene, followed by CH!NH proton migration. In contrast, this reaction se-quence terminates at the first step in the case of the antimony analogue 2,t hus giving the 1-stiba-1,4-dihydro-iminonaphthalenes 7 and 8.R eactions of the bismuth congener 3 gave one of two products depending on the alkyne used. Reactiono f3 with DMAD gave 1-bisma-1,4-dihydro-iminonaphthalene 9,w hilst its reactionw ith two equivalents of HCC(CO 2 Me) gave bismacyclohexadiene (10). All compounds have been characterized by NMR, IR, and Raman spectroscopiesa nd X-ray diffraction analysis. The experimental data were complemented by ac omputational study,i ncludingadescription of the reaction profileso ft he hetero-DA reactions and an assessment of the aromaticitieso ft he heterocyclic naphthalene derivatives. Scheme1.Example of theb isma-DA reaction producing bisma[2.2.2]bicyclooctadiene (A). Formation of 1-arsanaphthalenethrough the intermediate (INT)f ormed by arsa-DA reaction (B); Dip = 2,6-(iPr) 2 C 6 H 3 .[a] Ing.

show abstract

An Isolable Bismabenzene: Synthesis, Structure, and Reactivity

Cited by 42 publications

References 38 publications

Rational design of near‐infrared absorbing organic dyes: Controlling the HOMO–LUMO gap using quantitative molecular orbital theory

Rational design of near‐infrared absorbing organic dyes: Controlling the HOMO–LUMO gap using quantitative molecular orbital theory

A One‐Step Germole to Silole Transformation and a Stable Isomer of a Disilabenzene

Hetero Diels–Alder Reactions of Masked Dienes Containing Heavy Group 15 Elements

Contact Info

Product

Resources

About