Protonation of CH3N3 and CF3N3 in Superacids: Isolation and Structural Characterization of Long‐Lived Methyl‐ and Trifluoromethylamino Diazonium Ions

0525622 - ÚOCHB 2021 RIV DE eng J - Journal Article
Saal, T. - Blastik, Zsófia E. - Haiges, R. - Nirmalchandar, A. - Baxter, A. F. - Christe, K. O. - Vasiliu, M. - Dixon, D. A. - Beier, Petr - Prakash, G. K. S.
Protonation of CH3N3 and CF3N3 in Superacids: Isolation and Structural Characterization of Long‐Lived Methyl‐ and Trifluoromethylamino Diazonium Ions.
Angewandte Chemie - International Edition. Roč. 59, č. 30 (2020), s. 12520-12526. ISSN 1433-7851. E-ISSN 1521-3773
R&D Projects: GA MŠMT LTAUSA18037
Institutional support: RVO:61388963
Keywords : azidomethane * azidotrifluoromethane * diazonium salts * protonation * superacids
OECD category: Organic chemistry
Impact factor: 15.336, year: 2020
Method of publishing: Limited access
https://onlinelibrary.wiley.com/doi/full/10.1002/anie.202002750

The methylamino diazonium cations [CH3N(H)N-2](+) and [CF3N(H)N-2](+) were prepared as their low-temperature stable [AsF6](-) salts by protonation of azidomethane and azidotrifluoromethane in superacidic systems. They were characterized by NMR and Raman spectroscopy. Unequivocal proof of the protonation site was obtained by the crystal structures of both salts, confirming the formation of alkylamino diazonium ions. The Lewis adducts CH3N3.AsF5 and CF3N3.AsF5 were also prepared and characterized by low-temperature NMR and Raman spectroscopy, and also by X-ray structure determination for CH3N3.AsF5. Electronic structure calculations were performed to provide additional insights. Attempted electrophilic amination of aromatics such as benzene and toluene with methyl- and trifluoromethylamino diazonium ions were unsuccessful.
Permanent Link: http://hdl.handle.net/11104/0309727