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 - Článek v odborném periodiku
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
Grant CEP: GA MŠMT LTAUSA18037
Institucionální podpora: RVO:61388963
Klíčová slova: azidomethane * azidotrifluoromethane * diazonium salts * protonation * superacids
Obor OECD: Organic chemistry
Impakt faktor: 15.336, rok: 2020
Způsob publikování: Omezený přístup
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.
Trvalý link: http://hdl.handle.net/11104/0309727