Studying the dimerization reaction during the abstraction of halogen from organohalides by laser photoemission, controlled-potential electrolysis, and voltammetry

Thermodynamic and kinetic characteristics of intermediates of electrode reactions: Determination by direct and combined electrochemical methods

“…resolved voltammograms for a trifluoromethyl radical. By their appearance these are close to TRV for other organic radicals described in [1,32,111].…”

“…A group of methods of laser photoemission (LPE), 2 which were designed in the 1960s to 1990s (see, for example, [1,33,85,86,89]) and the references presented there, getting technically ever more perfect [1,32,39,40,83,, continues to be actively used for both the investigation of irreversible and quasi-reversible electrode reactions involving intermediates in aprotic and protogenic media [1,39,40,84,87,88,[98][99][100][101][102][103][104][105][106][107][108][109][110][111] and the investigation of redox properties of intermediates in aprotic media [1,[94][95][96][97].…”

“…4a, curve 1). The situation turns more involved in the presence of a slow chemical τ X 1 -step, for example, the dissociation of radical anions [87,88,122] or the formation/dissociation of a metastable complex of radicals with a donor/acceptor of protons [32,[100][101][102], which is possible in both protic and aprotic media; the latter case is presented in Fig. 4a, curve 2, for a metastable complex of radical β-hydroxyethyl with H 3 O + [100].…”

“…In particular, detailed investigation of redox properties of intermediates has already made it possible to explain why a number of reactions expected a priori do not occur in reality, for example, the cross-coupling of radicals during the photoreduction of benzophenone by 2propanol [6][7][8] or the dimerization of radical β -hydroxyethyl to 1,4-butanediol in media from acid to weakly alkaline [32]. On the other hand, on the basis of the above information it happened to be possible to efficiently control certain practically important electrosyntheses, for…”

Electrode reactions and electroanalysis of organomercury compounds

“…However, the fact of appearance of colloidal, finely dispersed (or dropped) mercury was conventionally assumed 192 ± 198 to be evidence of the OMC formation. Correspondingly, this type of degradation of cathodes made of different materials accompanied by the formation of organometallic compounds 2 was also observed (for instance, in the electrolysis of BuI at Zn, Hg and Sn electrodes and also at a Pb electrode where Bu 3 PbI could even be isolated 198 ). The indirect evidence of the involvement of the mercury electrode in the depolarizer electroreduction was believed to include the appearance of additional signals in voltammograms that were absent at other electrode and also the easier electroreduction at mercury as compared with electrocatalytically inactive electrodes 199 ± 201 (GC, boron-doped and fluorinated borondoped diamond electrode, see, e.g., Ref.…”