Reactivity of Diarylnitrenium Ions

Abstract

Hydride abstraction from diarylamines with the trityl ion is explored in an attempt to generate a stable diarylnitrenium ion, Ar2N+. Sequential H‐atom abstraction reactions ensue. The first H‐atom abstraction leads to intensely colored aminium radical cations, Ar2NH.+, some of which are quite stable. However, most undergo a second H‐atom abstraction leading to ammonium ions, Ar2NH2+. In the absence of a ready source of H‐atoms, a unique self‐abstraction reaction occurs when Ar=Me5C6, 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.