title: Ionization of aniline and its N-methyl and N-phenyl substituted derivatives by (free) electron transfer to n-butyl chloride parent radical cations.
abstract: The electron transfer from aniline and its N-methyl as well as N-phenyl substituted derivatives (N-methylaniline, N,N-dimethylaniline, diphenylamine, triphenylamine) to parent solvent radical cations was studied by electron pulse radiolysis in n-butyl chloride solution. The ionization results in the case of aniline (ArNH2) and the secondary aromatic amines (Ar2NH, Ar(Me)NH) in the synchronous and direct formation of amine radical cations, as well as aminyl radicals, in comparable amounts. Subsequently, ArNH2*+ deprotonates in a delayed reaction with the present nucleophile Cl-, and forms further ArNH*. In contrast, tertiary aromatic amines such as triphenylamine and dimethylaniline yield primarily the corresponding amine radical cations Ar3N*+ or Ar(Me2)N*+, only. The persistent Ar3N*+ forms a charge transfer complex (dimer) with the parent amine molecule, whereas Ar(Me2)N*+ deprotonates to carbon-centered radicals Ar(Me)NCH2*.
authors.affiliation: University of Leipzig, Interdisciplinary Group Time-Resolved Spectroscopy, Permoserstrasse 15, D-04303 Leipzig, Germany.
authors.forename: Andrej
authors.initials: A
authors.lastname: Maroz
authors.forename: Ralf
authors.initials: R
authors.lastname: Hermann
authors.forename: Sergej
authors.initials: S
authors.lastname: Naumov
authors.forename: Ortwin
authors.initials: O
authors.lastname: Brede