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...
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| Main Authors: | , |
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| Format: | Article |
| Language: | English |
| Published: |
2024
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| Subjects: | |
| Online Access: | https://hdl.handle.net/10356/173359 |
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| Institution: | Nanyang Technological University |
| Language: | English |
| Summary: | 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. |
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