Crystalline 2π aromatic azadiboriridinylium: a BN analogue of cyclopropenylium cation
N-Substitution of a thermally unstable diboratriazole 1 with a trimethylsilyl group affords a remarkably stable diboratriazole derivative 2. Ring contraction of 2 with an N-heterocyclic carbene accompanied by the release of N2 as well as 1,4-hydrogen shift affords a carbene-stabilized azadiboriridin...
| Main Authors: | , |
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| Other Authors: | |
| Format: | Journal Article |
| Language: | English |
| Published: |
2024
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| Online Access: | https://hdl.handle.net/10356/173359 |
| _version_ | 1826114668933939200 |
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| author | Zhu, Lizhao Kinjo, Rei |
| author2 | School of Chemistry, Chemical Engineering and Biotechnology |
| author_facet | School of Chemistry, Chemical Engineering and Biotechnology Zhu, Lizhao Kinjo, Rei |
| author_sort | Zhu, Lizhao |
| collection | NTU |
| description | N-Substitution of a thermally unstable diboratriazole 1 with a trimethylsilyl group affords a remarkably stable diboratriazole derivative 2. Ring contraction of 2 with an N-heterocyclic carbene accompanied by the release of N2 as well as 1,4-hydrogen shift affords a carbene-stabilized azadiboriridine 3. Abstraction of the H-B3mem hydride in 3 with methyl trifluoromethanesulfonate leads to the isolation of a hitherto unknown azadiboriridinylium 4, the first BN analogue of cyclopropenylium cation. X-ray diffraction analysis and computational studies confirmed the delocalization of π electrons over the B2 N three-membered ring, indicating the 2π aromatic feature. Compound 4 undergoes ring expansion reactions with azobenzene and pyridazine to furnish triazadiborolidinylium species 5 and 6, the latter of which possesses a cationic B2 N3 ring with a pronounced 6π aromatic property. Moreover, the reaction of 4 with a diazo compound produces a cationic B2 N3 C pentafulvene derivative 7. |
| first_indexed | 2024-10-01T03:42:54Z |
| format | Journal Article |
| id | ntu-10356/173359 |
| institution | Nanyang Technological University |
| language | English |
| last_indexed | 2024-10-01T03:42:54Z |
| publishDate | 2024 |
| record_format | dspace |
| spelling | ntu-10356/1733592024-03-11T08:03:57Z Crystalline 2π aromatic azadiboriridinylium: a BN analogue of cyclopropenylium cation Zhu, Lizhao Kinjo, Rei School of Chemistry, Chemical Engineering and Biotechnology Aromatic Cation N-Substitution of a thermally unstable diboratriazole 1 with a trimethylsilyl group affords a remarkably stable diboratriazole derivative 2. Ring contraction of 2 with an N-heterocyclic carbene accompanied by the release of N2 as well as 1,4-hydrogen shift affords a carbene-stabilized azadiboriridine 3. Abstraction of the H-B3mem hydride in 3 with methyl trifluoromethanesulfonate leads to the isolation of a hitherto unknown azadiboriridinylium 4, the first BN analogue of cyclopropenylium cation. X-ray diffraction analysis and computational studies confirmed the delocalization of π electrons over the B2 N three-membered ring, indicating the 2π aromatic feature. Compound 4 undergoes ring expansion reactions with azobenzene and pyridazine to furnish triazadiborolidinylium species 5 and 6, the latter of which possesses a cationic B2 N3 ring with a pronounced 6π aromatic property. Moreover, the reaction of 4 with a diazo compound produces a cationic B2 N3 C pentafulvene derivative 7. Nanyang Technological University National Research Foundation (NRF) We are grateful to Nanyang Technological University (NTU), the National Research Foundation, Singapore (NRF‐NRFI07‐2021‐0002), and Nippon Shokubai, for financial support. 2024-01-30T00:45:52Z 2024-01-30T00:45:52Z 2023 Journal Article Zhu, L. & Kinjo, R. (2023). Crystalline 2π aromatic azadiboriridinylium: a BN analogue of cyclopropenylium cation. Angewandte Chemie, 62(47), e202312949-. https://dx.doi.org/10.1002/anie.202312949 1433-7851 https://hdl.handle.net/10356/173359 10.1002/anie.202312949 37828652 2-s2.0-85174693922 47 62 e202312949 en NRF-NRFI07-2021-0002 Angewandte Chemie International Edition © 2023 Wiley-VCH GmbH. All rights reserved. |
| spellingShingle | Aromatic Cation Zhu, Lizhao Kinjo, Rei Crystalline 2π aromatic azadiboriridinylium: a BN analogue of cyclopropenylium cation |
| title | Crystalline 2π aromatic azadiboriridinylium: a BN analogue of cyclopropenylium cation |
| title_full | Crystalline 2π aromatic azadiboriridinylium: a BN analogue of cyclopropenylium cation |
| title_fullStr | Crystalline 2π aromatic azadiboriridinylium: a BN analogue of cyclopropenylium cation |
| title_full_unstemmed | Crystalline 2π aromatic azadiboriridinylium: a BN analogue of cyclopropenylium cation |
| title_short | Crystalline 2π aromatic azadiboriridinylium: a BN analogue of cyclopropenylium cation |
| title_sort | crystalline 2π aromatic azadiboriridinylium a bn analogue of cyclopropenylium cation |
| topic | Aromatic Cation |
| url | https://hdl.handle.net/10356/173359 |
| work_keys_str_mv | AT zhulizhao crystalline2paromaticazadiboriridinyliumabnanalogueofcyclopropenyliumcation AT kinjorei crystalline2paromaticazadiboriridinyliumabnanalogueofcyclopropenyliumcation |