Indirect Electrolysis. Reaction between Alkyl Halides and Electrolytically Generated Anion Radicals.

Alkylation of [2,2′-([2,2′-bipyridine]-6,6′-diyl)bis[phenolato]-N,N′,O,O′]nickel(II) during catalytic reduction of 1-iodooctane

“…Indeed the cyclic voltammetric behavior observed in Fig. 2 for compound 1 in the presence of 1-iodooctane is similar to results obtained for various aromatic compounds in the presence of organic halides [35,41]. Alternatively, Ni(II)L ÅÀ could also react directly with the alkyl halide in an S N 2 fashion to produce a modified species and halide ion as shown in reaction (8).…”

“…As shown in reaction (6), 1 could be produced in a reduced form, Ni(II)L ÅÀ , that exhibits ligand-radical character rather than nickel(I) character, whereupon Ni(II)L ÅÀ could interact with an alkyl radical to form a modified species (reaction (7)). This radical-coupling mechanism has been reported extensively in investigations of the homogeneous reduction of organic halides via electrogenerated aromatic radical anions [35][36][37][38][39][40][41]. Indeed the cyclic voltammetric behavior observed in Fig.…”

Electrocarboxylation of Benzyl Halides through Redox Catalysis on the Preparative Scale

“…The occurrence of this side reaction [Eq. (25)] has been recognized since the earliest works on redox catalysis [22,23] and more recently it has been used profitably to determine the reduction potential of a wide series of organic radicals. [24] Indeed, the full occurrence of the process shown in Equation (25) corresponds to the complete depletion of M and to the quantitative formation of E-M-R by a twoelectron route compared with M, while full occurrence of the reduction portrayed in Equation (17), followed by the coupling of R À with the electrophile E + , corresponds to total conservation of M and to the formation of R-E by a two-electron route compared with RX, that is, formally a 1 + 2([RX]/[M])-electron route compared with M. Thus, the determination of the relative yields in E-M-R, M, and R-E at the end of an electrolysis, or of the charge consumed, or of the current used in analytical electrochemistry are direct measurements of the competition parameter q.…”

Oxidation and Reduction of Halogen‐containing Compounds

“…Other early investigations involved the catalytic reduction of 1-bromo-and 1-chlorobutane by the anion radicals of trans-stilbene and anthracene [132], of 1-chlorohexane and 6-chloro-1-hexene by the naphthalene anion radical [133], and of 1-chlorooctane by the phenanthrene anion radical [134]. Simonet and coworkers [135] pointed out that a catalytically formed alkyl radical can react with an aromatic anion radical to form an alkylated aromatic hydrocarbon. Additional, comparatively recent work has centered on electron transfer between aromatic anion radicals and 1,2-dichloro-1,2-diphenylethane [136], on reductive coupling of tert-butyl bromide with azobenzene, quinoxaline, and anthracene [137], and on the reactions of aromatic anion radicals with substituted benzyl chlorides [138], with vinyl bromides, 2-bromoindene, and 7,7-dichlorobicyclo[4.1.0]heptane [139], and with bornyl, isobornyl, and exo-and endonorbornyl bromides [140].…”