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Stabilization of the Dual-Aromatic cyclo-N5– Anion by Acidic Entrapment
- Source :
- The Journal of Physical Chemistry Letters. 10:2378-2385
- Publication Year :
- 2019
- Publisher :
- American Chemical Society (ACS), 2019.
-
Abstract
- Pentazole anion, the best candidate for full-nitrogen energetic materials, can be isolated only from acidic solution for unclear reasons, which hinders the high-yield realization of a full-nitrogen substance with higher energy density. Herein, we report for the first time the discovery of the dual aromaticity (π and σ) of cyclo-N5–, which makes the anion unstable in nature but confers additional stability in acidic surroundings. In addition to the usual π-aromaticity, similar to that of the prototypical benzene, five lone pairs are delocalized in the equatorial plane of cyclo-N5–, forming additional σ-aromaticity. It is the compatible coexistence of the inter-lone-pair repulsion and inter-lone-pair attraction within the σ-aromatic system that makes the naked cyclo-N5– highly reactive to electrophiles and easily broken. Only in sufficiently acid solution can the cyclo-N5– become unsusceptible to the electrophilic attack and gain extra stability through the formation of hydrogen-bonded complex from surrounding electrophiles; otherwise, the cyclo-N5– cannot be productively isolated. The dual aromaticity discovered in cyclo-N5– is expected to be universal for pnictogen five-membered ring systems. Accepted version Financial support from the National Natural Science Foundation of China (Nos. 11604017, 11572053, and U1730244), the Science Challenging Program of China (No. TZ2016001), and the National Supercomputing Center (Shenzhen) and helpful discussions with B.C. Hu, M. Gozin, M. Š ob, E. Hayward, C.Y. Zhang, J.G. Zhang and H.H. Zong are gratefully acknowledged.
- Subjects :
- Chemistry
Pentazole
Aromaticity
02 engineering and technology
010402 general chemistry
021001 nanoscience & nanotechnology
Ring (chemistry)
01 natural sciences
Dual Aromaticity
0104 chemical sciences
Delocalized electron
chemistry.chemical_compound
Computational chemistry
Electrophile
Electrical and electronic engineering [Engineering]
General Materials Science
Physical and Theoretical Chemistry
0210 nano-technology
Benzene
Pnictogen
Lone pair
Pentazole Anion
Subjects
Details
- ISSN :
- 19487185
- Volume :
- 10
- Database :
- OpenAIRE
- Journal :
- The Journal of Physical Chemistry Letters
- Accession number :
- edsair.doi.dedup.....2669b74941be17ae454790c4cadb6b81