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
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.
Angew Chem Int Ed Engl. 2020 Jul 20;59(30):12520-12526. doi: 10.1002/anie.202002750. Epub 2020 Jun 3.
The methylamino diazonium cations [CH N(H)N ] and [CF N(H)N ] were prepared as their low-temperature stable [AsF ] 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 N ⋅AsF and CF N ⋅AsF were also prepared and characterized by low-temperature NMR and Raman spectroscopy, and also by X-ray structure determination for CH N ⋅AsF . 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.
通过在超酸性体系中使叠氮甲烷和叠氮三氟甲烷质子化，制备了甲氨基重氮阳离子[CH₃N(H)N₂⁺]和[CF₃N(H)N₂⁺]，其形式为低温稳定的[AsF₆⁻]盐。通过核磁共振（NMR）和拉曼光谱对它们进行了表征。通过两种盐的晶体结构明确了质子化位点，证实了烷基氨基重氮离子的形成。还制备了路易斯加合物CH₃N₂·AsF₅和CF₃N₂·AsF₅，并通过低温核磁共振和拉曼光谱以及CH₃N₂·AsF₅的X射线结构测定对其进行了表征。进行了电子结构计算以提供更多见解。尝试用甲基和三氟甲基氨基重氮离子对苯和甲苯等芳烃进行亲电胺化反应未成功。
