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Chemistry. 2020 Mar 16. doi: 10.1002/chem.202000930. [Epub ahead of print]

Reactivity of diarylnitrenium ions.

Author information

1
University of Tartu, Institute of Chemisty, Ravila 14A, 50411, Tartu, ESTONIA.
2
Eidgenossische Technische Hochschule Zurich, Department of Chemistry and applied bioscience, SWITZERLAND.
3
Tartu Ulikool, Institute of Chemistry, ESTONIA.
4
University of California Riverside, Department of Chemistry, UNITED STATES.

Abstract

Hydride abstraction from diarylamines with 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.

KEYWORDS:

Nitrenium ion, bulky substituents, aminium radical cation, iminium radical cation, triplet

PMID:
32180268
DOI:
10.1002/chem.202000930

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