Ionization of Aniline and ItsN-methyl andN-phenyl Substituted Derivatives by (Free) Electron Transfer ton-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*.

Sulfur rich electron donors – formation of singlet versus triplet radical ion pair states featuring different lifetimes in the same conjugate

“…35,36 The ability of BuCl˙ + oxidizing aromatic amines via free electron transfer is well established in the literature. 37,38 So it is safe to assume that 2 and 3 are oxidized like TPA – described in the literature as forming 2 ˙ + and 3 ˙ + , respectively. 37 …”

“…37,38 So it is safe to assume that 2 and 3 are oxidized like TPA – described in the literature as forming 2 ˙ + and 3 ˙ + , respectively. 37 …”

Perfluoroalkylation reactions of (hetero)arenes

“…[17][18][19][20][21][22][23][24] Hereby, polypyridyl organometallic complexes, such as [Ru(bpy) 3 Cl 2 ], are activated by visible light and have proven to be mild and more sustainable alternatives for traditional photochemistry utilizing UV energy. [17][18][19][20][21][22][23][24] Hereby, polypyridyl organometallic complexes, such as [Ru(bpy) 3 Cl 2 ], are activated by visible light and have proven to be mild and more sustainable alternatives for traditional photochemistry utilizing UV energy.…”

“…5-8 C Ar-H peruoroalkyl-group radical substitution reactions of arenes can be classied into thermal and photoinduced methods. [12][13][14][15][16][17][18] Photoinduced methods either through direct homolysis of X-C n F 2n+1 bonds, 19,20 or by means of photoinduced electron transfer (PET) reactions 21 are capable of generating per-uoroalkyl radicals C n F 2n+1 even in aqueous systems 22 (Fig. 1) or else be non-metal catalyzed, among which, the use of the Baran reagent 14 or per-uoroalkylsulnate salts 15 in the presence of organic peroxide 16 or azo initiators 17 (Fig.…”

Hidden chemistry of substituted aniline radical cations in water: a mechanistic study

“…They are often discussed in many application areas such as biochemical synthesis, dye, pesticide and drug industries, stabilization of polymers, and plastics. One of the main reasons for showing such properties is the relatively weak O–H and N–H bond in phenols and amines, respectively . Because of low bond energy ( D N–H ) 80–85 kcal mol −1 , the primary and secondary amines act as H donors in radical reactions .…”