Controlled Generation of 9‐Boratriptycene by Lewis Adduct Dissociation: Accessing a Non‐Planar Triarylborane

Chardon, Aurélien; Osi, Arnaud; Mahaut, Damien; Doan, Thu‐Hong; Tumanov, Nikolay; Wouters, Jan; Fusaro, Luca; Champagne, Benoı̂t; Berionni, Guillaume

doi:10.1002/anie.202003119

Cited by 54 publications

(69 citation statements)

References 59 publications

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“… M06‐2X/6–311G(d) gas phase fluoride ion affinities (FIA, Δ H 0 in kJ mol −1 ), affinities with ammonia and triphenylphosphine (Gibbs free energies, Δ G 0 in kJ mol −1 ), global (ω, in eV) and local (boron, ω B , in eV) electrophilicity indexes of the borane derivatives 9 a – d and 4 a – d . As a comparison, the corresponding affinities (in kJ mol −1 ) of B(C 6 F 5 ) 3 for F − (Δ H 0 ), NH 3 (Δ G 0 ) and PPh 3 (Δ G 0 ) are −466, −117 and −62 respectively while its global and local electrophilicity indexes are, respectively 2.79 eV and −1.23 eV [23] . In parenthesis are indicated the reorganization energies necessary for the borane to reach its final geometry in the Lewis adduct.…”

Section: Resultsmentioning

confidence: 99%

Methylene Bridging Effect on the Structures, Lewis Acidities and Optical Properties of Semi‐planar Triarylboranes

Doan

Chardon

Osi

et al. 2020

Chemistry A European J

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Three synthetic methods towards semi‐planar triarylboranes with two aryl rings connected by a methylene bridge have been developed. The fine‐tuning of their stereoelectronic properties and Lewis acidities was achieved by introducing fluorine, methyl, methoxy, n‐butyl and phenyl groups either at their exocyclic or bridged aryl rings. X‐ray diffraction analysis and quantum‐chemical calculations provided quantitative information on the structural distortion experienced by the near planar hydro‐boraanthracene skeleton during the association with Lewis bases such as NH3 and F−. Though the methylene bridge between the ortho‐positions of two aryl rings of triarylboranes decreased the Gibbs free energies of complexation with small Lewis bases by less than 5 kJ mol−1 relative to the classical Lewis acid BAr3, the steric shielding of the CH2 bridge is sufficient to avoid the formation of Lewis adducts with larger Lewis bases such as triarylphosphines. A newly synthesized spirocyclic amino‐borane with a long intramolecular B−N bond that could be dissociated under thermal process, UV‐irradiation, or acidic conditions might be a potential candidate in Lewis pairs catalysis.

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Section: Resultsmentioning

confidence: 99%

Methylene Bridging Effect on the Structures, Lewis Acidities and Optical Properties of Semi‐planar Triarylboranes

Doan

Chardon

Osi

et al. 2020

Chemistry A European J

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“…Similarly, 20 years later, the same group described the formation of BPh 3 upon heating different tetraarylborate salts to at least 200 °C [67] . Tetraarylborates are used on rare occasions to this day as valuable, alternative precursors to triarylboranes [68–70] …”

Section: Synthesis Of Symmetrically Substituted Triarylboranesmentioning

confidence: 99%

“…[67] Tetraarylborates are used on rare occasions to this day as valuable, alternative precursors to triarylboranes. [68][69][70] Based on this work, Brown et al re-synthesized tri-a-naphthylborane 10 as ar eference Lewis acid to estimate the Lewis base strength of primary,s econdary,a nd tertiary amines, [71] having slightly modified the synthesiso ft he triarylborane. To make the synthesis safer,B rown and co-workersu sed boron trifluoride etherate( BF 3 •OEt 2 )i nstead of gaseous boron trifluoride.…”

Section: Boron Trifluoride As the Boron Sourcementioning

confidence: 99%

Synthetic Approaches to Triarylboranes from 1885 to 2020

Berger

Ferger

Marder

2021

Chemistry A European J

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In recent years, research in the fields of optoelectronics, anion sensors and bioimaginga gents have been greatly influenced by novel compounds containing triarylborane motifs. Such compounds possess an empty p-orbital at boron which resultsi nu seful optical and electronic properties. Such ad iversity of applications was not expected when the first triarylboranew as reported in 1885. Synthetic approaches to triarylboranes underwent variousc hanges over the following century,s ome of which are still used in the present day,s uch as the generally applicable routes developedb yK rause et al. in 1922developedb yK rause et al. in , or by Grisdale et al. in 1972 at Eastman Kodak. Some other developments were not pursued further after their initial reports, such as the synthesis of two triarylboranes bearing three different aromatic groups by Mikhailov et al. in 1958. This reviews ummarizes the developmento fs ynthetic approaches to triarylboranes from their first report nearly 135 years ago to the present.2021 The Authors. Chemistry -A European Journal published by Wiley-VCH GmbH. This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided the original work is properlyc ited.Selected by the EditorialO ffice for our Showcaseo fo utstanding Reviewtype articles (www.chemeurj.org/showcase).

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“…3a-c,13 Mikhailov realized such a structural motif by the synthesis of 1-boraadamantane, 14,15 while Berionni et al released a non-planar 9-boratriptycene (D) by in situ protonolysis of corresponding borate-complexes [R4P][tBuC6H4-D] with HNTf2 in CH2Cl2 (Tf = O2SCF3). 16 In the resulting mixture, D is in an association-dissociation equilibrium with the weakly coordinating [NTf2]ion and was isolated in the form of its trapping products with various N-, P-, or O-centered Lewis bases. 17 Structural data from X-ray crystallography are not available for either free 1-boraadamantane or D. Gas-phase electron diffraction on 3-methyl-1-boraadamantane at 100 °C revealed that the B atom in the equilibrium structure has a (slightly) pyramidal configuration with Σ(C-B-C) = 349.4(4)° and av.…”

Section: Introductionmentioning

confidence: 99%