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Reactivity of Diarylnitrenium Ions
Author(s) -
Kütt Agnes,
Jeschke Gunnar,
Toom Lauri,
Nerut Jaak,
Reed Christopher A.
Publication year - 2020
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.202000930
Subject(s) - iminium , chemistry , ion , abstraction , reactivity (psychology) , atom (system on chip) , hydride , photochemistry , hydrogen atom abstraction , radical , medicinal chemistry , organic chemistry , hydrogen , computer science , parallel computing , medicine , philosophy , alternative medicine , epistemology , pathology
Hydride abstraction from diarylamines with the trityl ion is explored in an attempt to generate a stable diarylnitrenium ion, Ar 2 N + . Sequential H‐atom abstraction reactions ensue. The first H‐atom abstraction leads to intensely colored aminium radical cations, Ar 2 NH .+ , some of which are quite stable. However, most undergo a second H‐atom abstraction leading to ammonium ions, Ar 2 NH 2 + . In the absence of a ready source of H‐atoms, a unique self‐abstraction reaction occurs when Ar=Me 5 C 6 , leading to a novel iminium radical cation, Ar=N .+ Ar, which decays via a second self H‐atom abstraction reaction to give a stable iminium ion, Ar=N + HAr. These products differ substantially from those derived via photochemically produced diarylnitrenium ions.