Generation of N,N-Di(4-bromophenyl)nitrenium Ion Under Acidic Conditions: Search for a Nitrenium Dication

Abstract

<jats:p>The behavior of the N,N-di(4-bromophenyl)nitrenium ion under acidic aqueous conditions was examined via laser flash photolysis experiments. A long-lived species forms and can be assigned as the cation radical or the dication. This species is unreactive towards nucleophiles and reactive towards strong electron donors, consistent with a cation radical. Mechanistic analysis indicates its formation is through a separate pathway than that of the nitrenium ion, suggestive of a triplet mechanism.</jats:p>

Generation ofN,N-Di(4-bromophenyl)nitrenium Ion under Acidic Conditions: Search for a Nitrenium Dication

“…An alternative excited state pathway for the formation of 3 is proposed. An initial version of this work was deposited on the ChemRxiv on 10 Mar 2020 …”

“…An initial version of this work was deposited on the ChemRxiv on 10 Mar 2020. 16 ■ RESULTS AND DISCUSSION LFP Generation of Nitrenium Ion 2 at Varying pHs. Figure 1 (top) shows the transient absorption spectrum resulting from pulsed laser (355 nm, 50 mJ/pulse, 7 ns) photolysis of pyridinium ion 1 in aqueous solution.…”

Photochemical generation and characterization of the 5-endo-10,11-dihydrodibenzoazepine nitrenium ion

“…Previous studies of other diarylnitrenium ions have shown some level of radical cation formation under certain conditions [48]. These have been attributed to reactions of nitrenium ion triplet states and/or branching from the initially formed pyridinium excited states.…”