Reactivity of Diarylnitrenium Ions. Issue 41 (7th July 2020)

• Record Type: Journal Article
• Authors: Kütt, Agnes; Jeschke, Gunnar; Toom, Lauri; Nerut, Jaak; Reed, Christopher A.
• Is Part Of: Chemistry. Volume 26:Issue 41(2020)
• Page Start: 8871
• Page End: 8874
• Publication Date: 2020-07-07
• Subjects: aminium radical cation -- bulky substituents -- iminium radical cations -- nitrenium ion -- triplet; Chemistry -- Periodicals; 540
• DOI: 10.1002/chem.202000930
• Languages: English
• ISSNs: 0947-6539

Abstract

Abstract: Hydride abstraction from diarylamines with the trityl ion is explored in an attempt to generate a stable diarylnitrenium ion, Ar2 N + . Sequential H‐atom abstraction reactions ensue. The first H‐atom abstraction leads to intensely colored aminium radical cations, Ar2 NH .+, some of which are quite stable. However, most undergo a second H‐atom abstraction leading to ammonium ions, Ar2 NH2 + . In the absence of a ready source of H‐atoms, a unique self‐abstraction reaction occurs when Ar=Me5 C6, 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. Abstract : Nitrenium conundrum : When exploring synthetic‐scale generation of stable diarylnitrenium ions, Ar2 N +, we find products quite different to those derived from photochemical generation.