U.S. Department of Energy Office of Scientific and Technical Information
Protonation of CH 3 N 3 and CF 3 N 3 in Superacids: Isolation and Structural Characterization of Long‐Lived Methyl‐ and Trifluoromethylamino Diazonium Ions
Journal Article·· Angewandte Chemie (International Edition)
Loker Hydrocarbon Research Institute and Department of Chemistry University of Southern California University Park Los Angeles CA 90089-1661 USA
Institute of Organic Chemistry and Biochemistry of the Czech Academy of Sciences Flemingovo nam. 2 160 00 Prague 6 Czech Republic, Department of Organic Chemistry Faculty of Science Charles University Hlavova 2030/8 128 43 Prague Czech Republic
Department Chemistry The University of Alabama Tuscaloosa AL 35487 USA
Institute of Organic Chemistry and Biochemistry of the Czech Academy of Sciences Flemingovo nam. 2 160 00 Prague 6 Czech Republic
The methylamino diazonium cations [CH 3 N(H)N 2 ] + and [CF 3 N(H)N 2 ] + were prepared as their low‐temperature stable [AsF 6 ] − 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 CH 3 N 3 ⋅AsF 5 and CF 3 N 3 ⋅AsF 5 were also prepared and characterized by low‐temperature NMR and Raman spectroscopy, and also by X‐ray structure determination for CH 3 N 3 ⋅AsF 5 . 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.
Saal, Thomas, et al. "Protonation of CH <sub>3</sub> N <sub>3</sub> and CF <sub>3</sub> N <sub>3</sub> in Superacids: Isolation and Structural Characterization of Long‐Lived Methyl‐ and Trifluoromethylamino Diazonium Ions." Angewandte Chemie (International Edition), vol. 59, no. 30, Jun. 2020. https://doi.org/10.1002/anie.202002750
Saal, Thomas, Blastik, Zsófia E., Haiges, Ralf, Nirmalchandar, Archith, Baxter, Amanda F., Christe, Karl O., Vasiliu, Monica, Dixon, David A., Beier, Petr, & Prakash, G. K. Surya (2020). Protonation of CH <sub>3</sub> N <sub>3</sub> and CF <sub>3</sub> N <sub>3</sub> in Superacids: Isolation and Structural Characterization of Long‐Lived Methyl‐ and Trifluoromethylamino Diazonium Ions. Angewandte Chemie (International Edition), 59(30). https://doi.org/10.1002/anie.202002750
Saal, Thomas, Blastik, Zsófia E., Haiges, Ralf, et al., "Protonation of CH <sub>3</sub> N <sub>3</sub> and CF <sub>3</sub> N <sub>3</sub> in Superacids: Isolation and Structural Characterization of Long‐Lived Methyl‐ and Trifluoromethylamino Diazonium Ions," Angewandte Chemie (International Edition) 59, no. 30 (2020), https://doi.org/10.1002/anie.202002750
@article{osti_1631879,
author = {Saal, Thomas and Blastik, Zsófia E. and Haiges, Ralf and Nirmalchandar, Archith and Baxter, Amanda F. and Christe, Karl O. and Vasiliu, Monica and Dixon, David A. and Beier, Petr and Prakash, G. K. Surya},
title = {Protonation of CH <sub>3</sub> N <sub>3</sub> and CF <sub>3</sub> N <sub>3</sub> in Superacids: Isolation and Structural Characterization of Long‐Lived Methyl‐ and Trifluoromethylamino Diazonium Ions},
annote = {Abstract The methylamino diazonium cations [CH 3 N(H)N 2 ] + and [CF 3 N(H)N 2 ] + were prepared as their low‐temperature stable [AsF 6 ] − 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 CH 3 N 3 ⋅AsF 5 and CF 3 N 3 ⋅AsF 5 were also prepared and characterized by low‐temperature NMR and Raman spectroscopy, and also by X‐ray structure determination for CH 3 N 3 ⋅AsF 5 . 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. },
doi = {10.1002/anie.202002750},
url = {https://www.osti.gov/biblio/1631879},
journal = {Angewandte Chemie (International Edition)},
issn = {ISSN 1433-7851},
number = {30},
volume = {59},
place = {Germany},
publisher = {Wiley Blackwell (John Wiley & Sons)},
year = {2020},
month = {06}}