1,2‐Azaborine: The Boron‐Nitrogen Derivative of <i>ortho</i>‐Benzyne

Brough, Sarah A.; Lamm, Ashley N.; Liu, Shih‐Yuan; Bettinger, Holger F.

doi:10.1002/ange.201502967

Cited by 27 publications

(1 citation statement)

References 51 publications

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“…The corresponding Dewar isomer 6 was also obtained as an oil; however, it was quite readily hydrolyzed by trace amounts of water. As 5 is a thermal precursor to a BN aryne studied by matrix isolation techniques, we also investigated its photochemistry in an argon matrix. Photolysis of 5 with 280–400 nm irradiation quickly led to the formation of the Dewar valence isomer, based on the comparison of experimental and computed IR spectra, as the only photo product.…”

Section: Methodsmentioning

confidence: 99%

The Dewar Isomer of 1,2‐Dihydro‐1,2‐azaborinines: Isolation, Fragmentation, and Energy Storage

et al. 2018

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The photochemistry of 1,2‐dihydro‐1,2‐azaborinine derivatives was studied under matrix isolation conditions and in solution. Photoisomerization occurs exclusively to the Dewar valence isomers upon irradiation with UV light (>280 nm) with high quantum yield (46 %). Further photolysis with UV light (254 nm) results in the formation of cyclobutadiene and an iminoborane derivative. The thermal electrocyclic ring‐opening reaction of the Dewar valence isomer back to the 1,2‐dihydro‐1‐tert‐butyldimethylsilyl‐2‐mesityl‐1,2‐azaborinine has an activation barrier of (27.0±1.2) kcal mol−1. In the presence of the Wilkinson catalyst, the ring opening occurs rapidly and exothermically (ΔH=(−48±1) kcal mol−1) at room temperature.

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Section: Methodsmentioning

confidence: 99%

The Dewar Isomer of 1,2‐Dihydro‐1,2‐azaborinines: Isolation, Fragmentation, and Energy Storage

et al. 2018

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A Modular Synthetic Approach to Monocyclic 1,4‐Azaborines

Liu

Zhang

et al. 2016

Angewandte Chemie

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A simple and general method for the synthesis of a wide range of monocyclic 1,4-azaborines, including the first examples containing B heteroatoms is described. Post-heterocycle-formation olefin isomerization was employed as a key strategy. This new synthetic method provides fundamental insight into the resonance stabilization and photophysical properties of 1,4-azaborines.Scheme 1. Development of 1,4-azaborines.Scheme 2. Retrosynthetic analysis.

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Poly(iminoborane): Eine schwer fassbare Klasse von anorganischen Hauptgruppenpolymeren?

et al. 2016

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Der hohe Stellenwert anorganischer Hauptgruppenpolymere spiegelt sich wohl am deutlichsten in der wirtschaftlichen Bedeutung von Polysiloxanen (Siliconen) wider. Bororganische Materialien wie p-konjugierte Organoboranpolymere oder BN-dotierte polycyclische aromatische Kohlenwasserstoffe erregen derzeit große Aufmerksamkeit. Daher ist es verwunderlich, dass Poly(iminoborane) (PIBs), [BRNR'] n ,d ie Stammverbindungen ungesättigter B-N-Polymere,d ie formal mit Polyacetylen isoelektronischs ind, bis heute noch nicht eindeutig charakterisiert worden waren. Hier stellen wir die Synthese und umfassende Charakterisierung eines linearen Oligo(iminoborans) vor,das aus einer Kette von durchschnittlich 12-14 BN-Einheiten besteht. Durch unseren Syntheseansatz werden unerwünschte Nebenreaktionen, in denen Borazine gebildet werden, effektiv unterbunden. Unterstützende DFT-u nd TD-DFT-Rechnungen verschaffen einen tieferen Einblick in die Mikrostruktur und die elektro-nischeS truktur des Oligomers. Hintergrundinformationen zu diesem Beitrag sind unter: http://dx.Schema 2. (a) Synthese von Oligo(iminoboran) 4 und dessen Endgruppen-modifiziertemDerivat 4'.(b) Synthese der Modellverbindung 7 (Oct = n-C 8 H 17 ).

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1,2‐Azaborine: The Boron‐Nitrogen Derivative of ortho‐Benzyne

Cited by 27 publications

References 51 publications

The Dewar Isomer of 1,2‐Dihydro‐1,2‐azaborinines: Isolation, Fragmentation, and Energy Storage

The Dewar Isomer of 1,2‐Dihydro‐1,2‐azaborinines: Isolation, Fragmentation, and Energy Storage

A Modular Synthetic Approach to Monocyclic 1,4‐Azaborines

Poly(iminoborane): Eine schwer fassbare Klasse von anorganischen Hauptgruppenpolymeren?

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