A crystalline B₄N₂ dewar benzene as a building block for conjugated B,N-chains
Dewar benzene, one of the isolable valence isomers of C6H6, has been extensively studied since its first synthesis in 1962. By contrast, the chemistry of inorganic congeners of Dewar benzene, which can be formally gained by replacing the skeletal carbon atoms with heteroatoms, has been less develope...
Saved in:
Main Authors: | , |
---|---|
Other Authors: | |
Format: | Article |
Language: | English |
Published: |
2022
|
Subjects: | |
Online Access: | https://hdl.handle.net/10356/159344 |
Tags: |
Add Tag
No Tags, Be the first to tag this record!
|
Institution: | Nanyang Technological University |
Language: | English |
id |
sg-ntu-dr.10356-159344 |
---|---|
record_format |
dspace |
spelling |
sg-ntu-dr.10356-1593442023-02-28T20:11:08Z A crystalline B₄N₂ dewar benzene as a building block for conjugated B,N-chains Ota, Kei Kinjo, Rei School of Physical and Mathematical Sciences Science::Chemistry Crystal Atomic Structure Density Functional Theory Dewar benzene, one of the isolable valence isomers of C6H6, has been extensively studied since its first synthesis in 1962. By contrast, the chemistry of inorganic congeners of Dewar benzene, which can be formally gained by replacing the skeletal carbon atoms with heteroatoms, has been less developed despite their peculiar structural and electronic features. Among them, the extant B,N-Dewar benzenes are limited to the B3N3 system. Herein, we report the development of the first example of an isolable B4N2 Dewar benzene, 3. As predicted by DFT calculations, a judicious selection of the substituents allows synthesizing 3. Single-crystal X-ray analysis, NMR, and computational studies confirmed that 3 possesses a high-lying B(sp3)-B(sp3) σ-bond at the bridgehead position. Reactions with ethylene and phenylacetylene proceeded smoothly under mild conditions, affording the fused B4C4N2 ring systems (4 and 5). Structural characterization as well as DFT calculations revealed that compounds 4 and 5 involve a rigid and conjugated (BN)4 tetraene scaffold. Formation of 4 and 5 demonstrates that 3 may serve as a building block for the construction of conjugated B,N-chains. Ministry of Education (MOE) Nanyang Technological University Submitted/Accepted version This work was financially supported by Nanyang Technological University (NTU), Singapore, and the Singapore Ministry of Education (MOE2018-T2-048(S)) (R.K.). 2022-06-15T01:10:17Z 2022-06-15T01:10:17Z 2021 Journal Article Ota, K. & Kinjo, R. (2021). A crystalline B₄N₂ dewar benzene as a building block for conjugated B,N-chains. Journal of the American Chemical Society, 143(29), 11152-11159. https://dx.doi.org/10.1021/jacs.1c04860 0002-7863 https://hdl.handle.net/10356/159344 10.1021/jacs.1c04860 34264664 2-s2.0-85111258397 29 143 11152 11159 en MOE2018-T2-048(S) Journal of the American Chemical Society This document is the Accepted Manuscript version of a Published Work that appeared in final form in Journal of the American Chemical Society, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://doi.org/10.1021/jacs.1c04860 application/pdf |
institution |
Nanyang Technological University |
building |
NTU Library |
continent |
Asia |
country |
Singapore Singapore |
content_provider |
NTU Library |
collection |
DR-NTU |
language |
English |
topic |
Science::Chemistry Crystal Atomic Structure Density Functional Theory |
spellingShingle |
Science::Chemistry Crystal Atomic Structure Density Functional Theory Ota, Kei Kinjo, Rei A crystalline B₄N₂ dewar benzene as a building block for conjugated B,N-chains |
description |
Dewar benzene, one of the isolable valence isomers of C6H6, has been extensively studied since its first synthesis in 1962. By contrast, the chemistry of inorganic congeners of Dewar benzene, which can be formally gained by replacing the skeletal carbon atoms with heteroatoms, has been less developed despite their peculiar structural and electronic features. Among them, the extant B,N-Dewar benzenes are limited to the B3N3 system. Herein, we report the development of the first example of an isolable B4N2 Dewar benzene, 3. As predicted by DFT calculations, a judicious selection of the substituents allows synthesizing 3. Single-crystal X-ray analysis, NMR, and computational studies confirmed that 3 possesses a high-lying B(sp3)-B(sp3) σ-bond at the bridgehead position. Reactions with ethylene and phenylacetylene proceeded smoothly under mild conditions, affording the fused B4C4N2 ring systems (4 and 5). Structural characterization as well as DFT calculations revealed that compounds 4 and 5 involve a rigid and conjugated (BN)4 tetraene scaffold. Formation of 4 and 5 demonstrates that 3 may serve as a building block for the construction of conjugated B,N-chains. |
author2 |
School of Physical and Mathematical Sciences |
author_facet |
School of Physical and Mathematical Sciences Ota, Kei Kinjo, Rei |
format |
Article |
author |
Ota, Kei Kinjo, Rei |
author_sort |
Ota, Kei |
title |
A crystalline B₄N₂ dewar benzene as a building block for conjugated B,N-chains |
title_short |
A crystalline B₄N₂ dewar benzene as a building block for conjugated B,N-chains |
title_full |
A crystalline B₄N₂ dewar benzene as a building block for conjugated B,N-chains |
title_fullStr |
A crystalline B₄N₂ dewar benzene as a building block for conjugated B,N-chains |
title_full_unstemmed |
A crystalline B₄N₂ dewar benzene as a building block for conjugated B,N-chains |
title_sort |
crystalline b₄n₂ dewar benzene as a building block for conjugated b,n-chains |
publishDate |
2022 |
url |
https://hdl.handle.net/10356/159344 |
_version_ |
1759854904486133760 |