Protonation of CH3 N3 and CF3 N3 in Superacids: Isolation and Structural Characterization of Long-Lived Methyl- and Trifluoromethylamino Diazonium Ions.
Angew Chem Int Ed Engl
; 59(30): 12520-12526, 2020 Jul 20.
Article
en En
| MEDLINE
| ID: mdl-32374510
ABSTRACT
The methylamino diazonium cations [CH3 N(H)N2 ]+ and [CF3 N(H)N2 ]+ 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 CH3 N3 â
AsF5 and CF3 N3 â
AsF5 were also prepared and characterized by low-temperature NMR and Raman spectroscopy, and also by X-ray structure determination for CH3 N3 â
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.
Texto completo:
1
Banco de datos:
MEDLINE
Idioma:
En
Año:
2020
Tipo del documento:
Article