Reactivity of diarylnitrenium ions.

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.