Reactivity of Diarylnitrenium Ions

Hydride ion from diarylamines with the trityl ion is explored in an attempt to generate a stable diarylnitrenium ion, Ar2N+. Sequential H‐atom ion reactions ensue. The first H‐atom ion leads to intensely colored aminium radical cations, Ar2NH.+, some of which are quite stable. However, most undergo...

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Bibliographic Details
Published in:Chemistry : a European journal 2020-07, Vol.26 (41), p.8871-8874
Main Authors: Kütt, Agnes, Jeschke, Gunnar, Toom, Lauri, Nerut, Jaak, Reed, Christopher A.
Format: Article
Language:English
Subjects:
aminium radical cation
Ammonium
bulky substituents
Cations
Chemistry
iminium radical cations
Ions
nitrenium ion
triplet
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Summary:Hydride ion from diarylamines with the trityl ion is explored in an attempt to generate a stable diarylnitrenium ion, Ar2N+. Sequential H‐atom ion reactions ensue. The first H‐atom ion leads to intensely colored aminium radical cations, Ar2NH.+, some of which are quite stable. However, most undergo a second H‐atom ion leading to ammonium ions, Ar2NH2+. In the absence of a ready source of H‐atoms, a unique self‐ion reaction occurs when Ar=Me5C6, leading to a novel iminium radical cation, Ar=N.+Ar, which decays via a second self H‐atom ion reaction to give a stable iminium ion, Ar=N+HAr. These products differ substantially from those derived via photochemically produced diarylnitrenium ions. Nitrenium conundrum: When exploring synthetic‐scale generation of stable diarylnitrenium ions, Ar2N+, we find products quite different to those derived from photochemical generation.
ISSN:0947-6539
1521-3765
DOI:10.1002/chem.202000930